Substrate processing apparatus, substrate processing method, and storage medium

ABSTRACT

Disclosed is a substrate processing apparatus including a dry processing unit and a controller. The dry processing unit includes: a chamber that accommodates the substrate; a supercritical processing liquid supply unit that supplies a supercritical processing liquid to the substrate; a heating unit that heats an inside of the chamber; and a discharge unit that discharges a fluid in the chamber from the chamber. The controller controls the supercritical processing liquid supply unit, the heating unit, and the discharge unit such that the supercritical processing liquid is supplied to the substrate before or after the substrate is accommodated in the chamber, the inside of the chamber is heated to change the supercritical processing liquid into a supercritical fluid or a subcritical fluid, and the supercritical fluid or the subcritical fluid is discharged from the chamber.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. patent application Ser. No.15/440,060, filed on Feb. 23, 2017, which claims priority from JapanesePatent Application Nos. 2016-040229 and 2016-040202 filed on Mar. 2,2016 and Mar. 2, 2016, respectively, the disclosures of which areincorporated herein in their entirety by reference.

TECHNICAL FIELD

The present disclosure relates to a substrate processing apparatus and asubstrate processing method. In addition, the present disclosure relatesto a storage medium that stores a program which, when executed, causes acomputer to execute the substrate liquid processing method of thepresent disclosure.

BACKGROUND

In a manufacturing process of a semiconductor device in which alaminated structure of an integrated circuit is formed on the surfaceof, for example, a semiconductor wafer (hereinafter referred to as a“wafer”) as a substrate, a liquid processing step is provided to processthe surface of the wafer using a liquid, for example, to remove finedust or a natural oxide film on the surface of the wafer surface with acleaning liquid such as, for example, a chemical liquid.

There has been known a supercritical processing method using a fluid ina supercritical or subcritical state (which may also be collectivelyreferred to as a “supercritical fluid”) when removing a liquid or thelike attached to the surface of the wafer in the liquid processingprocess.

When a liquid attached to the surface of the substrate surface ischanged to a supercritical fluid or a subcritical fluid, alcohol suchas, for example, isopropyl alcohol (IPA) (see, e.g., Japanese PatentLaid-open Publication No. 2013-179245), or hydrofluoroether (HFE) orhydrofluorocarbon (HFC) (see, e.g., Japanese Patent Laid-Open Nos.2011-187570 and 2014-022566) may be used as a liquid source for thesupercritical fluid or the subcritical fluid.

SUMMARY

A substrate processing apparatus of the present disclosure includes: adry processing unit that performs a dry processing to dry a substrate;and a controller that controls an operation of the dry processing unit.The dry processing unit includes: a chamber that accommodates thesubstrate; a supercritical processing liquid supply unit that includes areservoir that stores a supercritical processing liquid containinghydrofluoroolefin, and supplies the supercritical processing liquid tothe substrate; a heating unit that heats an inside of the chamber; and adischarge unit that discharges a fluid in the chamber from the chamber.The controller controls the supercritical processing liquid supply unit,the heating unit, and the discharge unit such that the supercriticalprocessing liquid is supplied to the substrate by the supercriticalprocessing liquid supply unit before or after the substrate isaccommodated in the chamber, the inside of the chamber is heated by theheating unit in a state where the substrate is accommodated in thechamber to change the supercritical processing liquid into asupercritical fluid or a subcritical fluid, and then, the supercriticalfluid or the subcritical fluid is discharged from the chamber by thedischarge unit.

The foregoing summary is illustrative only and is not intended to be inany way limiting. In addition to the illustrative aspects, embodiments,and features described above, further aspects, embodiments, and featureswill become apparent by reference to the drawings and the followingdetailed description.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view illustrating a configuration of a substrateprocessing apparatus according to an exemplary embodiment of the presentdisclosure.

FIG. 2 is a schematic plan view illustrating a configuration of asubstrate processing section provided in the substrate processingapparatus illustrated in FIG. 1.

FIG. 3A is a schematic plan view illustrating a configuration of asubstrate processing section provided in the substrate processingapparatus illustrated in FIG. 2.

FIG. 3B is a schematic cross-sectional view illustrating a configurationof the cleaning processing unit provided in the substrate processingsection illustrated in FIG. 2.

FIG. 4 is a schematic perspective view illustrating a configuration of adry processing unit provided in the substrate processing sectionillustrated in FIG. 2.

FIG. 5 is a schematic cross-sectional view illustrating a configurationof the dry processing unit provided in the substrate processing sectionillustrated in FIG. 2.

FIG. 6 is a schematic cross-sectional view illustrating a configurationof the dry processing unit provided in the substrate processing sectionillustrated in FIG. 2.

FIG. 7 is a schematic cross-sectional view illustrating a configurationof a substrate processed in the substrate processing apparatusillustrated in FIG. 1.

DETAILED DESCRIPTION

In the following detailed description, reference is made to theaccompanying drawing, which form a part hereof. The illustrativeembodiments described in the detailed description, drawing, and claimsare not meant to be limiting. Other embodiments may be utilized, andother changes may be made without departing from the spirit or scope ofthe subject matter presented here.

An OH group possessed by alcohol (e.g., IPA) may damage a substrate. TheOH group may oxidize, for example, tungsten in the substrate to generatetungsten oxide whiskers. Further, the OH group may etch silicon in thesubstrate and generate particles.

In addition, HFE and HFC may produce fluorine under a high temperatureand high pressure condition which is used for changing a liquid into asupercritical fluid or a subcritical fluid. The produced fluorine mayetch, for example, silicon in the substrate and causes thinning of thepattern of the substrate. Further, since fluorine-containing organicsolvents (e.g., HFE and HFC) are expensive, facilities for recovery andregeneration are required in order to reduce the manufacturing cost.

Therefore, a liquid other than alcohol, HFE, and HFC are demanded as aliquid serving as a source of the supercritical fluid or the subcriticalfluid.

Meanwhile, hydrofluoroolefins are small in global warming potential(GWP) and are easily decomposed by ultraviolet rays even when they areexhausted to the atmosphere as they are. In addition, thehydrofluoroolefins have both the property of being easily decomposed byultraviolet rays and the property of being hardly decomposed by heatingduring a supercritical processing.

Therefore, the present disclosure is to provide a substrate processingapparatus and a substrate processing method capable of drying asubstrate using a supercritical processing liquid containinghydrofluoroolefin as a liquid serving as a source of a supercriticalfluid or a subcritical fluid. Further, the present disclosure is toprovide a storage medium that stores a program which, when executed,cause a computer to execute the substrate liquid processing method.

The present disclosure includes the followings.

According to an aspect of the present disclosure, a substrate processingapparatus of the present disclosure includes: a dry processing unit thatperforms a dry processing to dry a substrate; and a controller thatcontrols an operation of the dry processing unit. The controllercontrols the supercritical processing liquid supply unit, the heatingunit, and the discharge unit such that the supercritical processingliquid is supplied to the substrate by the supercritical processingliquid supply unit before or after the substrate is accommodated in thechamber, the inside of the chamber is heated by the heating unit in astate where the substrate is accommodated in the chamber to change thesupercritical processing liquid into a supercritical fluid or asubcritical fluid, and then, the supercritical fluid or the subcriticalfluid is discharged from the chamber by the discharge unit. Thecontroller controls the supercritical processing liquid supply unit, theheating unit, and the discharge unit such that the supercriticalprocessing liquid is supplied to the substrate by the supercriticalprocessing liquid supply unit before or after the substrate isaccommodated in the chamber, the inside of the chamber is heated by theheating unit in a state where the substrate is accommodated in thechamber to change the supercritical processing liquid into asupercritical fluid or a subcritical fluid, and then, the supercriticalfluid or the subcritical fluid is discharged from the chamber by thedischarge unit.

In the above-described substrate processing apparatus, thehydrofluoroolefin is hydrochlorofluoroolefin.

In the above-described substrate processing apparatus, the dryprocessing unit further includes a recycling unit that regenerates aliquid from the fluid discharged by the discharge unit and supplies theregenerated liquid to the reservoir.

In the above-described substrate processing apparatus, the dryprocessing unit further includes a concentration adjusting unit thatadjusts a concentration of the supercritical processing liquid stored inthe reservoir, and the controller controls the recycling unit and theconcentration adjusting unit such that the liquid regenerated by therecycling unit is supplied to the reservoir, and then, the concentrationof the supercritical processing liquid stored in the reservoir isadjusted to a predetermined concentration.

In the above-described substrate processing apparatus, the dryprocessing unit further includes a substrate holding unit moving betweenan external position of the chamber and an internal position of thechamber in a state of holding the substrate, and the controller controlsthe supercritical processing liquid supply unit and the substrateholding unit such that the supercritical processing liquid is suppliedto the substrate held by the substrate holding unit when the substrateholding unit is positioned at the external position or the internalposition.

In the above-described substrate processing apparatus, the controllercontrols the supercritical processing liquid supply unit and thesubstrate holding unit such that the supercritical processing liquid issupplied to the substrate held by the substrate holding unit when thesubstrate holding unit is positioned at the external position, and thedry processing unit further includes a recycling unit that regenerates agas evaporated from the supercritical processing liquid supplied to thesubstrate held by the substrate holding unit when the substrate holdingunit is positioned at the external position and a liquid from the fluiddischarged by the discharge unit, and supplies the regenerated liquid tothe reservoir.

In the above-described substrate processing apparatus, the dryprocessing unit further includes a concentration adjusting unit thatadjusts a concentration of the supercritical processing liquid stored inthe reservoir, and the controller controls the recycling unit and theconcentration adjusting unit such that the liquid regenerated by therecycling unit is supplied to the reservoir, and then, the concentrationof the supercritical processing liquid stored in the reservoir isadjusted to a predetermined concentration.

In the above-described substrate processing apparatus, the supercriticalprocessing liquid contains an organic solvent having a boiling pointhigher than that of the hydrofluoroolefin.

In the above-described substrate processing apparatus, a dry preventingliquid for preventing the drying of the substrate is filled on thesurface of the substrate before the supercritical processing liquid issupplied to the surface of the substrate, the dry preventing liquidcontains an organic solvent, and the organic solvent contained in thedry preventing liquid and the organic solvent contained in thesupercritical processing liquid are the same in kind.

In the above-described substrate processing apparatus, the dryprocessing unit further includes a cooling unit that cools thesupercritical processing liquid stored in the reservoir.

According to another aspect, the present disclosure provides a substrateprocessing method for drying a substrate in a chamber. The methodincludes: supplying a supercritical processing liquid that containshydrofluoroolefin and is stored in a reservoir to the substrate unitbefore or after the substrate is accommodated in the chamber; heating aninside of the chamber in a state where the substrate is accommodated inthe chamber to change the supercritical processing liquid supplied tothe substrate into a supercritical fluid or a subcritical fluid; anddischarging the supercritical fluid or the subcritical fluid from thechamber.

In the above-described substrate processing method, thehydrofluoroolefin is hydrochlorofluoroolefin.

The above-described substrate processing method further includesregenerating a liquid discharged from the discharging the supercriticalfluid to supply the regenerated liquid to the reservoir.

The above-described substrate processing method further includesadjusting a concentration of the supercritical processing liquid storedin the reservoir to a predetermined concentration after the regeneratedliquid is supplied to the reservoir.

In the above-described substrate processing method, in the supplying thesupercritical liquid, the supercritical processing liquid stored in areservoir is supplied to the substrate unit before the substrate isaccommodated in the chamber, and the method further comprises:regenerating a gas evaporated from the supercritical processing liquidsupplied to the substrate in the supplying the supercritical processingliquid and a liquid from the fluid discharged in the discharging thesupercritical fluid or the subcritical fluid to supply the regeneratedliquids to the reservoir.

The above-described substrate processing method further includesadjusting a concentration of the supercritical processing liquid storedin the reservoir to a predetermined concentration after the regeneratedliquids are supplied to the reservoir.

In the above-described substrate processing method, the supercriticalprocessing liquid contains an organic solvent having a boiling pointhigher than that of the hydrofluoroolefin.

In the above-described substrate processing method, a dry preventingliquid for preventing the drying of the substrate is filled on thesurface of the substrate before the supercritical processing liquid issupplied, the dry preventing liquid contains an organic solvent, and theorganic solvent contained in the dry preventing liquid and the organicsolvent contained in the supercritical processing liquid are the same inkind.

The above-described substrate processing method further includes coolingthe supercritical processing liquid stored in the reservoir.

According to still another aspect, the present disclosure provides astorage medium that stores a program for controlling a substrateprocessing apparatus which, when executed, cause a computer to controlthe substrate liquid processing apparatus and execute theabove-described substrate liquid processing method.

According to an aspect of the present disclosure, a substrate processingapparatus of the present disclosure includes: a dry processing unit thatperforms a dry processing to dry a substrate; and a controller thatcontrols operations of the dry processing unit. The dry processing unitincludes: a chamber that accommodates the substrate; a chamber thataccommodates the substrate; a dialkyl ether supply unit that supplies aliquid dialkyl ether represented by R¹—O—R² (wherein R¹ and R² representthe same or different alkyl groups) to the substrate; a heating unitthat heats an inside of the chamber; and a discharge unit thatdischarges a fluid in the chamber from the chamber. The controllercontrols the dialkyl ether supply unit, the heating unit, and thedischarge unit such that the liquid dialkyl ether is supplied to thesubstrate by the dialkyl ether supply unit before or after the substrateis accommodated in the chamber, the inside of the chamber is heated bythe heating unit in a state where the substrate is accommodated in thechamber to change the supercritical processing liquid into asupercritical fluid or a subcritical fluid, and then, the supercriticalfluid or the subcritical fluid is discharged from the chamber by thedischarge unit.

In the above-described substrate processing apparatus, the liquiddialkyl ether is methyl tert-butyl ether.

In the above-described substrate processing apparatus, a dry preventingliquid for preventing the drying of the substrate is filled on thesurface of the substrate before the liquid dialkyl ether is supplied tothe surface of the substrate.

In the above-described substrate processing apparatus, the drypreventing liquid contains isopropyl alcohol.

In the above-described substrate processing apparatus, the drypreventing liquid contains propylene glycol monomethyl ether acetate.

In the above-described substrate processing apparatus, the dryprocessing unit further includes a substrate holding unit moving betweenan external position of the chamber and an internal position of thechamber in a state of holding the substrate, and the dialkyl ethersupply unit supplies the liquid dialkyl ether to the substrate held bythe substrate holding unit when the substrate holding unit is positionedat the external position or the internal position.

According to another aspect, the present disclosure provides a substrateprocessing method for drying a substrate in a chamber. The methodincludes: supplying a liquid dialkyl ether represented by R¹—O—R²(wherein R¹ and R² represent the same or different alkyl groups) to thesubstrate unit before or after the substrate is accommodated in thechamber; heating an inside of the chamber in a state where the substrateis accommodated in the chamber to change the liquid diethyl ethersupplied to the substrate into a supercritical fluid or a subcriticalfluid; and discharging the supercritical fluid or the subcritical fluidfrom the chamber.

In the above-described substrate processing method, the liquid dialkylether is methyl tert-butyl ether.

In the above-described substrate processing method, a dry preventingliquid is filled on the surface of the substrate before the liquiddialkyl ether is supplied.

In the above-described substrate processing method, the dry preventingliquid contains isopropyl alcohol.

In the above-described substrate processing method, the dry preventingliquid contains propylene glycol monomethyl ether acetate.

In the above-described substrate processing method, the supplying theliquid dialkyl ether includes: holding the substrate in a substrateholding unit that moves between an external position of the chamber andan internal position of the chamber, and supplying the liquid dialkylether to the substrate held by the substrate holding unit when thesubstrate holding unit is positioned at the external position or theinternal position.

According to still another aspect, the present disclosure provides astorage medium that stores a program for controlling a substrateprocessing apparatus which, when executed, cause a computer to controlthe substrate liquid processing apparatus and execute theabove-described substrate liquid processing method.

According to the present disclosure, a substrate processing apparatusand a substrate processing method capable of drying a substrate using asupercritical processing liquid containing hydrofluoroolefin as a liquidserving as a source of a supercritical fluid or a subcritical fluid, anda storage medium that stores a program which, when executed, cause acomputer to execute the substrate liquid processing method, areprovided.

According to the present disclosure, a substrate processing apparatusand a substrate processing method capable of drying a substrate using aliquid that does not contain OH-groups and fluorine as a liquid servingas a source of a supercritical fluid or a subcritical fluid, and astorage medium that stores a program which, when executed, cause acomputer to execute the substrate liquid processing method, areprovided.

Hereinafter, exemplary embodiments of the present disclosure will bedescribed with reference to the drawings.

<Configuration of Substrate Processing Apparatus>

Descriptions will be made on a configuration of a substrate processingapparatus according to an exemplary embodiment of the present disclosurewith reference to FIG. 1. FIG. 1 is a schematic view illustrating aconfiguration of a substrate processing apparatus according to anexemplary embodiment of the present disclosure.

As illustrated in FIG. 1, a substrate processing apparatus 1 accordingto an exemplary embodiment of the present disclosure includes asubstrate processing section 2 and a controller 3 that controlsoperations of the substrate processing section 2.

The substrate processing section 2 performs various processings on asubstrate. The various processings performed by the substrate processingsection 2 will be described later.

The controller 3 is, for example, a computer, and includes a maincontroller and a memory. The main controller is, for example, a centralprocessing unit (CPU), and controls the operations of the substrateprocessing section 2 by reading and executing a program stored in thememory. The memory is constituted by a memory device such as, forexample, a random access memory (RAM), a read only memory (ROM), or ahard disc, and stores a program that controls various processingsperformed in the substrate processing section 2. The program may berecorded in a computer-readable storage medium, and installed from thestorage medium to the memory. The computer-readable storage medium maybe, for example, a hard disc (HD), a flexible disc (FD), a compact disc(CD), a magnet optical disc (MO), or a memory card. The storage mediumstores a program for controlling a substrate processing apparatus which,when executed, cause a computer to control the substrate liquidprocessing apparatus and execute the above-described substrate liquidprocessing method.

<Configuration of Substrate Processing Section>

Next, a specific configuration of a substrate processing section 2 willbe described with reference to FIG. 2. FIG. 2 is a schematic plan viewillustrating a configuration of the substrate processing section 2. Thedotted lines in FIG. 2 indicate substrates.

The substrate processing section 2 performs various processings on thesubstrates. In the exemplary embodiment, substrate processings performedby the substrate processing section 2 include a cleaning processing forcleaning a substrate and a dry processing for drying the substrate afterthe cleaning processing (wet substrate).

The substrate processing section 2 includes a carry-in/out station 21and a processing station 22 provided adjacent to the carry-in/outstation 21.

The carry-in/out station 21 includes a placing unit 211 and a conveyingunit 212 provided adjacent to the placing unit 211.

The placing unit 211 places thereon a plurality of conveyance containereach accommodating a plurality of substrates in a horizontal state(hereinafter, referred to as a “carrier C”).

The conveying unit 212 is provided with a conveyance mechanism 213 and adelivery unit 214. The conveyance mechanism 213 is provided with aholding mechanism that holds the substrate, and is configured to bemovable in the horizontal direction and the vertical direction andpivotable about the vertical axis.

The processing station 22 includes cleaning processing units 4 thatperform a cleaning processing to clean substrates, and dry processingunits 5 that perform a dry processing to dry the substrates that havebeen subjected to the cleaning processing (wet substrates). In theexemplary embodiment, the number of cleaning processing units 4 providedin the processing station 22 is two (2) or more, but may be one (1). Thesame is applied to the dry processing units 5. In the exemplaryembodiment, the cleaning processing units 4 are arranged on one side ofa conveyance path 221 that extends in a predetermined direction, and thedry processing units 5 are arranged on the other side of the conveyancepath 221. However, the arrangement of the cleaning processing units 4and the dry processing unit 5 may be appropriately changed.

A conveyance mechanism 222 is provided in the conveyance path 221. Theconveyance mechanism 222 is provided with a holding mechanism that holdsthe substrate, and is configured to be movable in the horizontaldirection and the vertical direction and pivotable about the verticalaxis. The conveyance mechanism 222 may have a mechanism to suppressvaporization (evaporation) of a dry preventing liquid filled on thesurface of the substrate therefrom during the conveyance. Examples ofsuch a mechanism include a cooling mechanism that cools the drypreventing liquid on the substrate held by the conveyance mechanism 222,and a cover mechanism that suppresses contact of the dry preventingliquid on the substrate held by the conveyance mechanism 222 with theoutside air.

The substrate to be subjected to a substrate processing by the substrateprocessing section 2 is, for example, a substrate W on which aconcavo-convex pattern 100 including a convex portion 101 and a concaveportion 102 is formed as illustrated in FIG. 7. The substrate W is, forexample, a semiconductor wafer. Hereinafter, the substrate to besubjected to a substrate processing by the cleaning processing unit 4will be referred to as a “substrate W1,” the substrate which has beensubjected to the substrate processing by the cleaning processing unit 4(substrate to be subjected to a substrate processing by the dryprocessing unit 5) will be referred to as a “substrate W2,” and thesubstrate which has been subjected to the substrate processing by thedry processing unit 5 will be referred to as a “substrate W3.”

In the substrate processing section 2, the conveyance mechanism 213 ofthe carry-in/out station 21 conveys the substrates W1, W3 between acarrier C and the delivery unit 214. Specifically, the conveyancemechanism 213 takes out the substrate W1 from the carrier C placed onthe placing unit 211, and places the taken-out substrate W1 on thedelivery section 214. In addition, the conveyance mechanism 213 takesout the substrate W3 placed on the delivery unit 214 by the conveyancemechanism 222 of the processing station 22, and stores the substrate W3in the carrier C of the placing unit 211.

In the substrate processing section 2, the conveyance mechanism 222 ofthe carry-in/out station 22 conveys the substrates W1, W2, W3 betweenthe delivery unit 214 and the cleaning processing unit 4, between thecleaning processing unit 4 and the dry processing unit 5, and betweenthe dry processing unit 5 and the delivery unit 214. Specifically, theconveyance mechanism 222 takes out the substrate W1 placed on thedelivery unit 214, and carries the taken-out substrate W1 into thecleaning processing unit 4. Further, the conveyance mechanism 222 takesout the substrate W2 from the cleaning processing unit 4, and carriesthe taken-out substrate W2 into the dry processing unit 5. Further, theconveyance mechanism 222 takes out the substrate W3 from the dryprocessing unit 5, and places the taken-out substrate W3 on the deliveryunit 214.

<Configuration 01 of Cleaning Processing Unit>

Next, a configuration of the cleaning processing unit 4 will bedescribed with reference to FIG. 3A. FIG. 3A is a schematiccross-sectional view illustrating a configuration of the cleaningprocessing unit 4.

The cleaning processing unit 4 performs a cleaning processing on thesubstrate W1 carried into the cleaning processing unit 4. Deposits(e.g., particles and organic substances) attached to the surface of thesubstrate W1 may be removed from the surface of the substrate W1 by thecleaning processing. The substrate processing performed by the cleaningprocessing unit 4 is not particularly limited as long as the cleaningprocessing on the substrate W1 is included. Therefore, the processingperformed by the cleaning processing unit 4 may include processingsother than the cleaning processing. In the exemplary embodiment, thesubstrate processing performed by the cleaning processing unit 4includes, for example, a rinse processing and a dry preventing liquidsupply processing in addition to the cleaning processing.

The cleaning processing unit 4 includes a chamber 41, and performs thesubstrate processing including the cleaning processing in the chamber41.

The cleaning processing unit 4 includes a substrate holding unit 42. Thesubstrate holding unit 42 includes a rotary shaft 421 that extends inthe vertical direction in the chamber 41, a turntable 422 that isattached to the upper end of the rotary shaft 421, and a chuck 423 thatis provided on the outer peripheral portion of the upper surface of theturntable 422 and supports the outer edge portion of the substrate W1,and a driving unit 424 that rotationally drives the rotation shaft 421.

The substrate W1 is supported by the chuck 423 and held horizontally onthe turntable 422 in a state of being slightly separated from the uppersurface of the turntable 422. In the exemplary embodiment, the holdingmethod of the substrate W1 by the substrate holding unit 42 is aso-called mechanical chuck type method in which the outer edge portionof the substrate W1 is gripped by the movable chuck 423, but may be aso-called vacuum chuck type method in which the rear surface of thesubstrate W1 is vacuum-adsorbed.

A proximal end portion of the rotary shaft 421 is rotatably supported bythe driving unit 424, and a distal end portion of the rotary shaft 421horizontally supports the turntable 422. When the rotary shaft 421rotates, the turntable 422 attached to the upper end portion of therotary shaft 421 rotates, so that the substrate W1 held by the turntable422 rotates while being supported by the chuck 423. The controller 3controls the operation of the driving unit 424 to control, for example,the rotation timing, rotation speed, and rotation time of the substrateW1.

The cleaning processing unit 4 includes a cleaning liquid supply unit1043 a, a rinse liquid supply unit 1043 b, and a dry preventing liquidsupply unit 1043 c that supply a cleaning liquid 1L1, a rinse liquid1L2, and a dry preventing liquid 1L3, respectively, to the substrate W1held by the substrate holding unit 42. The controller 3 controls thecleaning liquid supply unit 1043 a, the rinse liquid supply unit 1043 b,and the dry preventing liquid supply unit 1043 c to control the rotationtiming, rotation speed, and rotation time of the various processingliquids.

The cleaning liquid supply unit 1043 a includes a nozzle 1431 a thatejects the cleaning liquid 1L1 to the substrate W1 held by the substrateholding unit 42, and a cleaning liquid source 1432 a that supplies thecleaning liquid 1L1 to the nozzle 1431 a. The cleaning liquid 1L1 isstored in a tank provided in the cleaning liquid source 1432 a. Thecleaning liquid 1L1 is supplied to the nozzle 1431 a from the cleaningliquid source 1432 a through a supply pipe line 1434 a in which a flowrate adjustor 1433 a (e.g., a valve) is interposed. Examples of thecleaning liquid 1L1 include an SC1 liquid (mixed liquid of ammonia andhydrogen peroxide) which is an alkaline chemical liquid, and a dilutehydrofluoric acid aqueous solution (DHF) which is an acidic chemicalliquid. The SC1 liquid may be used as a cleaning liquid to removedeposits such as, for example, particles and organic substances from thesurface of the substrate W1. The DHF may be used as a cleaning liquid toremove an oxide film from the surface of the substrate W1. The cleaningliquid supply unit 1043 a may be configured to separately supply two ormore kinds of cleaning liquids to the nozzle 1431 a.

The rinse liquid supply unit 1043 b includes a nozzle 1431 b that ejectsthe rinse liquid 1L2 to the substrate W1 held by the substrate holdingunit 42, and a rinse liquid source 1432 b that supplies the rinse liquid1L2 to the nozzle 1431 b. The rinse liquid 1L2 is stored in a tankprovided in the rinse liquid source 1432 b. The rinse liquid 1L2 issupplied to the nozzle 1431 b from the rinse liquid source 1432 bthrough a supply pipe line 1434 b in which a flow rate adjustor 1433 b(e.g., a valve) is interposed. Examples of the rinse liquid 1L2 includedeionized water (DIW).

The dry preventing liquid supply unit 1043 c includes a nozzle 1431 cthat ejects the dry preventing liquid 1L3 to the substrate W1 held bythe substrate holding unit 42, and a dry preventing liquid source 1432 cthat supplies the dry preventing liquid 1L3 to the nozzle 1431 c. Thedry preventing liquid 1L3 is stored in a tank provided in the rinseliquid source 1432 c. The dry preventing liquid 1L3 is supplied to thenozzle 1431 c from the dry preventing liquid source 1432 c through asupply pipe line 1434 c in which a flow rate regulator 1433 c (e.g., avalve) is interposed. The dry preventing liquid 1L3 may contain anorganic solvent. Examples of the organic solvent contained in the drypreventing liquid 1L3 include alcohol such as, for example, isopropylalcohol (IPA).

The cleaning processing unit 4 includes a nozzle moving mechanism 44that drives the nozzles 1431 a to 1431 c. The nozzle moving mechanism 44includes an arm 441, a moving body 442 with a built-in driving mechanismthat is movable along the arm 441, and a pivoting and lifting mechanism443 that pivots and lifts the arm 441. The nozzles 1431 a to 1431 c areattached to the movable body 442. The nozzle moving mechanism 44 is ableto move the nozzles 1431 a to 1431 c between an upper position of thecenter of the substrate W1 held by the substrate holding unit 42 and anupper position of the peripheral portion of the substrate W1.Furthermore, the nozzle moving mechanism 44 is able to move the nozzles1431 a to 1431 c to a standby position outside a cup 45 (to be describedlater) in a plan view. In the exemplary embodiment, the nozzles 1431 ato 1431 c are held by a common arm, but may be held by separate arms toindependently move.

The cleaning processing unit 4 includes a cup 45 having a discharge port451. The cup 45 is provided around the substrate holding unit 42, andreceives various processing liquids (e.g., the cleaning liquid, therinse liquid, and the dry preventing liquid) scattered from thesubstrate W1. The cup 45 is provided with a lifting mechanism 46 thatdrives the cup 45 in the vertical direction, and a liquid dischargemechanism 47 that collects the various processing liquids scattered fromthe substrate W1 in the discharge port 451 and discharges the collectedprocessing liquids therefrom.

The cleaning processing unit 4 may perform a single substrate typecleaning processing that cleans the substrates W1 one by one by spincleaning. The cleaning processing may be performed, for example, in thefollowing order: cleaning with SC1 liquid→rinsing with DIW→cleaning withDHF→rinsing with DIW. During the cleaning processing, the atmosphere inthe chamber 41 may be exhausted from an exhaust port (not illustrated).

<Configuration 02 of Cleaning Processing Unit>

Next, a configuration of the cleaning processing unit 4 will bedescribed with reference to FIG. 3B. FIG. 3B is a schematiccross-sectional view illustrating a configuration of the cleaningprocessing unit 4.

The cleaning processing unit 4 performs a cleaning processing on thesubstrate W1 carried into the cleaning processing unit 4. Deposits(e.g., particles and organic substances) attached to the surface of thesubstrate W1 may be removed from the surface of the substrate W1 by thecleaning processing. The substrate processing performed by the cleaningprocessing unit 4 is not particularly limited as long as the cleaningprocessing on the substrate W1 is included. Therefore, the processingperformed by the cleaning processing unit 4 may include processingsother than the cleaning processing. In the exemplary embodiment, thesubstrate processing performed by the cleaning processing unit 4includes, for example, a rinse processing and a dry preventing liquidsupply processing in addition to the cleaning processing.

The cleaning processing unit 4 includes a chamber 41, and performs thesubstrate processing including the cleaning processing in the chamber41.

The cleaning processing unit 4 includes a substrate holding unit 42. Thesubstrate holding unit 42 includes a rotary shaft 421 that extends inthe vertical direction in the chamber 41, a turntable 422 that isattached to the upper end of the rotary shaft 421, and a chuck 423 thatis provided on the outer peripheral portion of the upper surface of theturntable 422 and supports the outer edge portion of the substrate W1,and a driving unit 424 that rotationally drives the rotation shaft 421.

The substrate W1 is supported by the chuck 423 and held horizontally onthe turntable 422 in a state of being slightly separated from the uppersurface of the turntable 422. In the exemplary embodiment, the holdingmethod of the substrate W1 by the substrate holding unit 42 is aso-called mechanical chuck type method in which the outer edge portionof the substrate W1 is gripped by the movable chuck 423, but may be aso-called vacuum chuck type method in which the rear surface of thesubstrate W1 is vacuum-adsorbed.

A proximal end portion of the rotary shaft 421 is rotatably supported bythe driving unit 424, and a distal end portion of the rotary shaft 421horizontally supports the turntable 422. When the rotary shaft 421rotates, the turntable 422 attached to the upper end portion of therotary shaft 421 rotates, so that the substrate W1 held by the turntable422 rotates while being supported by the chuck 423. The controller 3controls the operation of the driving unit 424 to control, for example,the rotation timing, rotation speed, and rotation time of the substrateW1.

The cleaning processing unit 4 includes a cleaning liquid supply unit2043 a, a rinse liquid supply unit 2043 b, a first dry preventing liquidsupply unit 2043 c, and a second dry preventing liquid supply unit 2043d that supply a cleaning liquid 2L1, a rinse liquid 2L2, a first drypreventing liquid 2L3, and a second dry preventing liquid 2L4,respectively, to the substrate W1 held by the substrate holding unit 42.The controller 3 controls the cleaning liquid supply unit 2043 a, therinse liquid supply unit 2043 b, the first dry preventing liquid supplyunit 2043 c, and the second dry preventing liquid supply unit 2043 d tocontrol the rotation timing, rotation speed, and rotation time of thevarious processing liquids. In the exemplary embodiment, the cleaningprocessing unit 4 includes the first dry preventing liquid supply unit2043 c and the second dry preventing liquid supply unit 2043 d. However,the cleaning processing unit 4 may not include the second dry preventingliquid supply unit 2043 d. In an exemplary embodiment in which thecleaning processing unit 4 includes the first dry preventing liquidsupply unit 2043 c and the second dry preventing liquid supply unit 2043d, a part of the first dry preventing liquid 2L3 filled on the surfaceof the substrate may be replaced with the second dry preventing liquid2L4. For example, in a case where IPA is used as the first drypreventing liquid supply unit 2043 c and PGMEA is used as the second drypreventing liquid supply unit 2043 d, when a part of the IPA filled onthe surface of the substrate is replaced with the PGMEA, the surface ofthe substrate is further suppressed from being dried as compared with acase of IPA alone. Thus, the function as a dry preventing liquid may beenhanced. Further, unlike IPA, PGMEA does not have an OH group. Thus,PGMEA does not form a Lewis acid or a complex with a metal such as, forexample, tungsten (W), and does not cause any damage such as W whisker.

The cleaning liquid supply unit 2043 a includes a nozzle 2431 a thatejects the cleaning liquid 2L1 to the substrate W1 held by the substrateholding unit 42, and a cleaning liquid source 2432 a that supplies thecleaning liquid 2L1 to the nozzle 2431 a. The cleaning liquid 2L1 isstored in a tank provided in the cleaning liquid source 2432 a. Thecleaning liquid 2L1 is supplied to the nozzle 2431 a from the cleaningliquid source 2432 a through a supply pipe line 2434 a in which a flowrate adjustor 2433 a (e.g., a valve) is interposed. Examples of thecleaning liquid 2L1 include a SC1 liquid (mixed liquid of ammonia andhydrogen peroxide) which is an alkaline chemical liquid, and a dilutehydrofluoric acid aqueous solution (DHF) which is an acidic chemicalliquid. The SC1 liquid may be used as a cleaning liquid to removedeposits such as, for example, particles and organic substances from thesurface of the substrate W1. The DHF may be used as a cleaning liquid toremove an oxide film from the surface of the substrate W1. The cleaningliquid supply unit 2043 a may be configured to separately supply two ormore kinds of cleaning liquids to the nozzle 2431 a.

The rinse liquid supply unit 2043 b includes a nozzle 2431 b that ejectsthe rinse liquid 2L2 to the substrate W1 held by the substrate holdingunit 42, and a rinse liquid source 2432 b that supplies the rinse liquid2L2 to the nozzle 2431 b. The rinse liquid 2L2 is stored in a tankprovided in the rinse liquid source 2432 b. The rinse liquid 2L2 issupplied to the nozzle 2431 b from the rinse liquid source 2432 bthrough a supply pipe line 2434 b in which a flow rate adjustor 2433 b(e.g., a valve) is interposed. Examples of the rinse liquid 2L2 includedeionized water (DIW).

The first dry preventing liquid supply unit 2043 c includes a nozzle2431 c that ejects the first dry preventing liquid 2L3 to the substrateW1 held by the substrate holding unit 42, and a dry preventing liquidsource 2432 c that supplies the first dry preventing liquid 2L3 to thenozzle 2431 c. The first dry preventing liquid 2L3 is stored in a tankprovided in the dry preventing liquid source 2432 c. The first drypreventing liquid 2L3 is supplied to the nozzle 2431 c from the drypreventing liquid source 2432 c through a supply pipe line 2434 c inwhich a flow rate regulator 2433 c (e.g., a valve) is interposed.Examples of the the dry preventing liquid 2L3 include alcohol such as,for example, isopropyl alcohol (IPA).

The second dry preventing liquid supply unit 2043 d includes a nozzle2431 d that ejects the second dry preventing liquid 2L4 to the substrateW1 held by the substrate holding unit 42, and a dry preventing liquidsource 2432 d that supplies the second dry preventing liquid 2L4 to thenozzle 2431 d. The second dry preventing liquid 2L4, which is differentin kind from the first dry preventing liquid 2L3, is stored in a tankprovided in the dry preventing liquid source 2432 d. The second drypreventing liquid 2L4 is supplied to the nozzle 2431 d from the drypreventing liquid source 2432 d through a supply pipe line 2434 d inwhich a flow rate regulator 2433 d (e.g., a valve) is interposed.Examples of the the dry preventing liquid 2L4 include alcohol such as,for example, propylene glycol monomethyl ether acetate (PGMEA).

The cleaning processing unit 4 includes a nozzle moving mechanism 44that drives the nozzles 2431 a to 2431 d. The nozzle moving mechanism 44includes an arm 441, a moving body 442 with a built-in driving mechanismthat is movable along the arm 441, and a pivoting and lifting mechanism443 that pivots and lifts the arm 441. The nozzles 2431 a to 2431 d areattached to the movable body 442. The nozzle moving mechanism 44 is ableto move the nozzles 2431 a to 2431 d between an upper position of thecenter of the substrate W1 held by the substrate holding unit 42 and anupper position of the peripheral portion of the substrate W1.Furthermore, the nozzle moving mechanism 44 is able to move the nozzles2431 a to 2431 d to a standby position outside a cup 45 (to be describedlater) in a plan view. In the exemplary embodiment, the nozzles 2431 ato 2431 d are held by a common arm, but may be held by separate arms toindependently move.

The cleaning processing unit 4 includes a cup 45 having a discharge port451. The cup 45 is provided around the substrate holding unit 42, andreceives various processing liquids (e.g., the cleaning liquid, therinse liquid, and the dry preventing liquid) scattered from thesubstrate W1. The cup 45 is provided with a lifting mechanism 46 thatdrives the cup 45 in the vertical direction, and a liquid dischargemechanism 47 that collects the various processing liquids scattered fromthe substrate W1 in the discharge port 451 and discharges the collectedprocessing liquids therefrom.

The cleaning processing unit 4 may perform a single substrate typecleaning processing that cleans the substrates W1 one by one by spincleaning. The cleaning processing may be performed, for example, in thefollowing order: cleaning with SC1 liquid→rinsing with DIW→cleaning withDHF→rinsing with DIW. During the cleaning processing, the atmosphere inthe chamber 41 may be exhausted from an exhaust port (not illustrated).

<Configuration 01 of Dry Processing Unit>

Next, a specific configuration of a dry processing unit 5 will bedescribed with reference to FIGS. 4 to 6. FIG. 4 is a schematicperspective view illustrating a configuration of the dry processing unit5, and FIGS. 5 and 6 are schematic cross-sectional views illustratingthe configuration of the dry processing unit 5.

The dry processing unit 5 performs a dry processing on the substrate W2which have been subjected to a substrate processing by the cleaningprocessing unit 4. The substrate W2 which have been subjected to asubstrate processing by the cleaning processing unit 4 is in a wet stateby the dry preventing liquid 1L3 filled on the surface thereof. Thesubstrate processing performed by the dry processing unit 5 is notparticularly limited as long as the dry processing is included.Therefore, the processing performed by the dry processing unit 5 mayinclude processings other than the dry processing.

The dry processing unit 5 includes a chamber 500, and performs thesubstrate processing including the dry processing in the chamber 500.Hydrofluoroolefin is liable to be decomposed by ultraviolet rays. Thus,in order to suppress hydrofluoroolefin from being decomposed byultraviolet rays before the supercritical processing, the dry processingchamber 500 may be made of an ultraviolet impermeable material.Alternatively, the dry processing chamber 500 may be subjected to asurface treatment that imparts ultraviolet impermeability.

The dry processing unit 5 includes a supercritical processing chamber510 provided in the dry processing chamber 500, and performs thesubstrate processing including the supercritical processing in thesupercritical processing chamber 510. The expression “supercriticalprocessing” is used to cover not only a process of changing a liquidinto a supercritical fluid but also a process of changing a liquid intoa subcritical fluid. Hydrofluoroolefin is liable to be decomposed byultraviolet rays. Thus, in order to suppress hydrofluoroolefin frombeing decomposed by ultraviolet rays before the supercriticalprocessing, the supercritical processing chamber 510 may be made of anultraviolet impermeable material. Alternatively, the supercriticalprocessing chamber 510 may be subjected to a surface treatment thatimparts ultraviolet impermeability.

The supercritical processing chamber 510 includes an inner space 511 andan opening 512 leading to the inner space 511. The inner space 511 andthe opening 512 are defined by the wall portion of the supercriticalprocessing chamber 510. The supercritical processing chamber 510 isconfigured to seal the inner space 511 by sealing the opening 512. Theinner space 511 is a space capable of accommodating the substrate W2. Inthe exemplary embodiment, since the substrate W2 is accommodated in theinner space 511 in a state of being held by a substrate holding portion531, the inner space 511 is a space capable of accommodating thesubstrate holding unit 531 that holds the substrate W2. The size of theinner space 511 is, for example, about 200 to 10,000 cm³. Thecarry-in/out of the substrate W2 into/from the internal space 511 isperformed through the opening 512.

The supercritical processing chamber 510 includes a pressure-resistantcontainer. Examples of the pressure-resistant container include apressure-resistant container made of a material having a high pressureresistance but a relatively low thermal conductivity such as, forexample, stainless steel, carbon steel, titanium, Hastelloy (registeredtrademark), or Inconel (registered trademark). An inner container madeof a material having higher thermal conductivity than that of thepressure-resistant container (e.g., aluminum, copper, aluminum nitride,or silicon carbide) is provided inside the pressure-resistant containerin a nested structure. The internal container may be heated. A thermalinsulation layer made of, for example, quartz or alumina is providedbetween the pressure-resistant container and the inner container, andonly the inner container is heated, so that the thermal responsivenessof the supercritical processing chamber 510 may be improved, and energyconsumption may be reduced.

The dry processing unit 5 includes the substrate holding unit 531 thatholds the substrate W2. The substrate holding unit 531 is configured tohold the substrate W2 transversely in a state of being immersed in aliquid (e.g., a supercritical processing liquid G supplied from a firstsupercritical processing liquid supply unit 57 a and/or a secondsupercritical processing liquid supply unit 57 b). Hydrofluoroolefin isliable to be decomposed by ultraviolet rays. Thus, in order to suppresshydrofluoroolefin from being decomposed by ultraviolet rays before thesupercritical processing, the substrate holding unit 531 may be made ofan ultraviolet impermeable material. Alternatively, the substrateholding unit 531 may be subjected to a surface treatment that impartsultraviolet impermeability.

The dry processing unit 5 includes a cover member 532 provided in thesubstrate holding unit 531. The cover member 532 is configured to sealthe opening 512 of the supercritical processing chamber 510 when thesubstrate holding portion 531 is accommodated in the inner space 511 ofthe supercritical processing chamber 510. Hydrofluoroolefin is liable tobe decomposed by ultraviolet rays. Thus, in order to suppresshydrofluoroolefin from being decomposed by ultraviolet rays before thesupercritical processing, the cover member 532 may be made of anultraviolet impermeable material. Alternatively, the cover member 532may be subjected to a surface treatment that imparts ultravioletimpermeability.

The dry processing unit 5 includes a transfer mechanism 56 that enablesthe substrate holding unit 531 to move between an external position ofthe supercritical processing chamber 510 (a position where the substrateW2 is delivered to and from the substrate holding unit 531) and aninternal position of the supercritical processing chamber 510 (aposition where the supercritical processing is performed on thesubstrate W2 held by the substrate holding unit 531). The transfermechanism 56 is a slide mechanism including a rail 561 extending in amovement direction of the substrate holding unit 531 and a slider 562with a built-in driving mechanism that travels on the rail 561, and isprovided on both sides of the substrate holding unit 531. The slider 562is connected to the cover member 532. Therefore, as the slider 562 movesalong the rail 561, the cover member 532 and the substrate holding unit531 connected to the cover member 532 also move along the rail 561.Specifically, when the slider 562 moves to one end portion of the rail561, the substrate holding unit 531 is able to move to the externalposition of the supercritical processing chamber 510. When the slider562 moves to the other end portion of the rail 561, the substrateholding unit 531 is able to move to the internal position of thesupercritical processing chamber 510.

The dry processing unit 5 includes a heating unit 52 that heats theinside of the supercritical processing chamber 510. The heating unit 52is a heater made of, for example, a heating resistor, and is provided inthe wall portion of the supercritical processing chamber 510. Theheating unit 52 may heat the substrate W2 in the supercriticalprocessing chamber 510 through heating of the inside of thesupercritical processing chamber 510. The heating unit 52 may change theheat generation amount by a power supplied from a power supply unit 521,and may increase the temperature in the supercritical processing chamber510 according to a predetermined heating schedule, based on, forexample, a temperature detection result acquired from a temperaturedetection unit 522 or a pressure detection result of a pressuredetection unit 513.

The dry processing unit 5 includes a first supercritical processingliquid supply unit 57 a that supplies a supercritical processing liquidG containing hydrofluoroolefin to the substrate W2 held by the substrateholding unit 531 when the substrate holding unit 531 is positioned atthe external position of the supercritical processing chamber 510, and asecond supercritical processing liquid supply unit 57 b that suppliesthe supercritical processing liquid G containing hydrofluoroolefin tothe substrate W2 held by the substrate holding unit 531 when thesubstrate holding unit 531 is positioned at an inner position of thesupercritical processing chamber 510. In the exemplary embodiment, thesupercritical processing liquid G supplied by the first supercriticalprocessing liquid supply unit 57 a and the supercritical processingliquid G supplied by the second supercritical processing liquid supplyunit 57 b have the same composition. Accordingly, the hydrofluoroolefincontained in the supercritical processing liquid G supplied by the firstsupercritical processing liquid supply unit 57 a and thehydrofluoroolefin contained in the supercritical processing liquid Gsupplied by the second supercritical processing liquid supply unit 57 bare the same in kind. When the supercritical processing liquid Gcontains an organic solvent, the organic solvent contained in thesupercritical processing liquid G supplied by the first supercriticalprocessing liquid supply unit 57 a and the organic solvent contained inthe supercritical processing liquid G supplied by the secondsupercritical processing liquid supply unit 57 b are the same in kind.In the exemplary embodiment in which the supercritical processing liquidG supplied by the first supercritical processing liquid supply unit 57 aand the supercritical processing liquid G supplied by the secondsupercritical processing liquid supply unit 57 b have the samecomposition, the liquid regenerated by a recycling unit 58 (to bedescribed later) may be reused as the supercritical processing liquid Gsupplied by the first supercritical processing liquid supply unit 57 aand/or the supercritical processing liquid G supplied by the secondsupercritical processing liquid supply unit 57 b (in the exemplaryembodiment, the supercritical processing liquid G supplied by the firstsupercritical processing liquid supply unit 57 a and the supercriticalprocessing liquid G supplied by the second supercritical processingliquid supply unit 57 b), without fractionation by, for example,distillation.

The dry processing unit 5 may include only one of the firstsupercritical processing liquid supply unit 57 a and the secondsupercritical processing liquid supply unit 57 b. In the exemplaryembodiment in which the dry processing unit 5 includes both of the firstsupercritical processing liquid supply unit 57 a and the secondsupercritical processing liquid supply unit 57 b, the position of thesubstrate holding unit 531 when the supercritical processing liquid G issupplied to the substrate W2 may be either the external position or theinternal position of the supercritical processing chamber 510. However,in an exemplary embodiment in which the dry processing unit includes thefirst supercritical processing liquid supply unit 57 a only, theposition of the substrate holding unit 531 when the supercriticalprocessing liquid G is supplied to the substrate W2 is the externalposition of the supercritical processing chamber 510. In an exemplaryembodiment in which the dry processing unit 5 includes the secondsupercritical processing liquid supply unit 57 b only, the position ofthe substrate holding unit 531 when the supercritical processing liquidG is supplied to the substrate W2 is the internal position of thesupercritical processing chamber 510.

The first supercritical processing liquid supply unit 57 a includes asupply pipe 571 a that ejects the supercritical processing liquid Gcontaining hydrofluoroolefin to the substrate W2 held by the substrateholding unit 531 when the substrate holding unit 531 is positioned atthe external position of the supercritical processing chamber 510, and areservoir 572 a that stores the supercritical processing liquid Gsupplied to the supply pipe 571 a. The supercritical processing liquid Gis stored in a tank provided in the reservoir 572 a. The supercriticalprocessing liquid G is supplied to the supply pipe 571 a from thereservoir 572 a through a flow rate adjustor 573 a (e.g., a valve).

The second supercritical processing liquid supply unit 57 b includes asupply pipe 571 b that ejects the supercritical processing liquid Gcontaining hydrofluoroolefin to the substrate W2 held by the substrateholding unit 531 when the substrate holding unit 531 is positioned atthe internal position of the supercritical processing chamber 510, and areservoir 572 b that stores the supercritical processing liquid Gsupplied to the supply pipe 571 b. The supercritical processing liquid Gis stored in a tank provided in the reservoir 572 b. The supercriticalprocessing liquid G is supplied to the supply pipe 571 b from thereservoir 572 a through a flow rate adjustor 573 b (e.g., a valve).

In the exemplary embodiment, the second supercritical processing liquidsupply unit 57 b ejects the supercritical processing liquid G directlyto the substrate W2 held by the substrate holding unit 531 when thesubstrate holding unit 531 is positioned at the internal position of thesupercritical processing chamber 510, but the supply embodiment of thesupercritical processing liquid G by the second supercritical processingliquid supply unit 57 b is not limited to the exemplary embodiment. Forexample, when the substrate holding unit 531 is positioned at theinternal position of the supercritical processing chamber 510, thesecond supercritical processing liquid supply unit 57 b may not ejectthe supercritical processing liquid G directly to the substrate W2 heldby the substrate holding unit 531, but eject the supercriticalprocessing liquid G to the bottom portion of the chamber 510 or thebottom portion of the substrate holding unit 531 that supports thesubstrate W2. Further, in the exemplary embodiment, the supercriticalprocessing liquid G supplied by the second supercritical processingliquid supply unit 57 b is liquid, but the phase of the supercriticalprocessing liquid G supplied from the second supercritical processingliquid supply unit 57 b is not limited to that in the exemplaryembodiment. For example, the supercritical processing liquid G suppliedfrom the second supercritical processing liquid supply unit 57 b may bein the form of a supercritical fluid or a subcritical fluid.

Olefin is an organic compound represented by C_(n)H_(2n) (n is aninteger of 2 or more), and has one double bond between C and C. Olefinis a class of unsaturated hydrocarbons and is also called alkene,ethylene-based hydrocarbon, or olefinic hydrocarbon. The carbon numberof the olefin is not particularly limited as long as it is 2 or more,but preferably 2 to 10, and more preferably 3 to 6. Examples of olefininclude CH₃—CH═CH₂ and CH₃—CH═CH—CH₃.

Hydrofluoroolefin (HFO) is a compound in which one or more hydrogenatoms of the olefin are substituted with fluorine atoms. The carbonnumber of the hydrofluoroolefin is not particularly limited, but ispreferably 1 to 10, and more preferably 2 to 6. The hydrofluoroolefinmay be either an E-form (trans form) or a Z-form (cis form). Thehydrofluoroolefin may be hydrochlorofluoroolefin (HCFO).Hydrochlorofluoroolefin is a compound in which one or more hydrogenatoms of the olefin are substituted with fluorine atoms and one or moreother hydrogen atoms of the olefin are substituted with chlorine atoms.The number of chlorine atoms in the hydrochlorofluoroolefin is notparticularly limited, but is preferably 1 to 5, and more preferably 1 to3. Examples of hydrofluoroolefins having no chlorine atom includeCF₃—CH═CH₂, CF₃—CF═CH₂, CHF₂—CH═CHF, CHF₂—CF═CH₂, CH₂F—CH═CF₂,CH₂F—CF═CHF, CH₃—CF═CF₂, CF₃—CH═CH—CF₃, CF₃—CH═CF—CH₃, CF₃—CF═CH—CH₃,CF₃—CH═CH—CH₂F, CHF₂—CF═CF—CH₃, CHF₂—CF═CH—CH₂F, CHF₂—CH═CF—CH₂F,CHF₂—CH═CH—CHF₂, CH₂F—CF═CF—CH₂F, CH₂F—CH═CH—CF₃, CH₂F—CF═CH—CHF₂,CF₃—CH₂—CF═CH₂, CF₃—CHF—CH═CH₂, CF₃—CH₂—CH═CHF, CHF₂—CF₂—CH═CH₂,CHF₂—CHF—CF═CH₂, CHF₂—CHF—CH═CHF, CH₂F—CF₂—CF═CH₂, CH₂F—CF₂—CH═CHF,CH₂F—CHF—CF═CHF, CH₂F—CHF—CF═CF₂, CH₂F—CH₂—CF═CF₂, CH₃—CF₂—CF═CHF, andCH₃—CF₂—CH═CF₂. Examples of hydrofluoroolefins having chlorine atoms(i.e., hydrochlorofluoroolefin) include CF₃—CH═CHCl, CHF₂—CF═CHCl,CHF₂—CH═CFCl, CHF₂—CCl═CHF, CH₂F—CCl═CF₂, CHFCl—CF═CHF, CH₂Cl—CF═CF₂,and CF₃—CCl═CH₂. Examples of commercially available hydrofluoroolefin(including hydrochlorofluoroolefin) include HFO DR2 (boiling point:33.4° C., critical temperature: 172° C., critical pressure: 2.9 MPa,GWP<10, IPA miscible) manufactured by Du Pont-Mitsui FluorochemicalsCo., Ltd., HFO DR12 (boiling point: 10° C., critical temperature: 138°C., critical pressure: 3.0 MPa, GWP 32) manufactured by Du Pont-MitsuiFluorochemicals Co., Ltd., HFO OPTEON 1234yf (boiling point: −29° C.,critical temperature: 95° C., critical pressure: 3.4 MPa, GWP 4)manufactured by Du Pont-Mitsui Fluorochemicals Co., Ltd, CCK-1105(boiling point: 18.4° C., critical temperature: 167° C., criticalpressure: 3.6 MPa, GWP 1, IPA miscible) manufactured by Central GlassCo., Ltd., and HCFO CGS-4 (boiling point: 39° C., critical temperatureand pressure are higher than those of DR2, GWP 4, IPA miscible)manufactured by Central Glass Co., Ltd.

The hydrofluoroolefin contained in the supercritical processing liquid Gmay be miscible with the dry preventing liquid 1L3. Thehydrofluoroolefin contained in the supercritical processing liquid G mayhave a critical temperature of 250° C. or less and a critical pressureof 10 MPa or less. In the hydrofluoroolefin contained in thesupercritical processing liquid G, the amount of fluorine generatedunder supercritical processing conditions is 1 ppm or less. Examples ofthe hydrofluoroolefin which satisfies these conditions include1-chloro-3,3,3-trifluoropropene (CF₃—CH═CHCl).1-Chloro-3,3,3-trifluoropropene is miscible with alcohol such as, forexample, IPA, and has a critical temperature of 167° C. and a criticalpressure of 3.6 MPa. 1-Chloro-3,3,3-trifluoropropene is desirable inthat its low global warming potential coefficient (GWP=1) does notrequire recovery of the exhaust gas and the waste liquid such as PFC,which is thus exhausted to the atmosphere as it is.

The supercritical processing liquid G may further contain, in additionto the hydrofluoroolefin, an organic solvent having a boiling pointhigher than that of the hydrofluoroolefin. When the supercriticalprocessing liquid G contains such an organic solvent, thehydrofluoroolefin is less likely to evaporate from the supercriticalprocessing liquid G as compared with a case where the organic solvent isnot contained. Thus, when the supercritical processing liquid G issupplied to the substrate W2, collapse of the concavo-convex pattern ofthe substrate W2 due to evaporation of the hydrofluoroolefin may beprevented. Examples of the organic solvent contained in thesupercritical processing liquid G include alcohol such as, for example,isopropyl alcohol. The amount of the organic solvent contained in thesupercritical processing liquid G may be set to the extent that thesupercritical processing liquid G becomes nonflammable under thesupercritical processing conditions. The volume ratio (organicsolvent:hydrofluoroolefin) of the organic solvent and thehydrofluoroolefin in the supercritical processing liquid G is preferably1:100 to 1:1, and more preferably 1:10 to 1:3. The organic solventcontained in the supercritical processing liquid G and the organicsolvent contained in the dry preventing liquid 1L3 may be the same inkind. When the organic solvent contained in the supercritical processingliquid G and the organic solvent contained in the dry preventing liquid1L3 may be the same in kind, the liquid regenerated by a recycling unit58 (to be described later) may be reused as the supercritical processingliquid G without fractionation by, for example, distillation.

The dry processing unit 5 includes a discharge unit 54 that dischargesthe fluid in the supercritical processing chamber 510. The dischargeunit 54 includes a discharge line 541 that discharges the fluid in thesupercritical processing chamber 510, and a flow rate adjustor 542(e.g., a valve) interposed in the discharge line 541. The flow rateadjustor 542 (e.g., a valve) adjusts the discharge amount of the fluidsuch that the inside of the supercritical processing chamber 510 isadjusted to a predetermined pressure.

The dry processing unit 5 includes a recycling unit 58 that regeneratesa liquid R from a gas evaporated from the supercritical processingliquid G supplied to the substrate W2 held by the substrate holding unit531 when the substrate holding unit 531 is positioned at the externalposition of the supercritical processing chamber 510, and a fluiddischarged from the discharge unit 54, and supplies the regeneratedliquid R to the reservoir 572 a of the first supercritical processingliquid supply unit 57 a and/or the reservoir 572 b of the secondsupercritical processing liquid supply unit 57 b (in the exemplaryembodiment, the reservoir 572 a of the first supercritical processingliquid supply unit 57 a and the reservoir 572 b of the secondsupercritical processing liquid supply unit 57 b).

The recycling unit 58 includes a discharge line 581 that discharges thefluid in the dry processing chamber 500, a flow rate adjustor 582 (e.g.,a valve) interposed in the discharge line 581, a liquid regenerator 583connected to the discharge line 581 and the discharge line 541 of thedischarge unit 54, a supply line 584 that supplies the liquid R, whichis regenerated from the liquid regenerator 583, to the reservoir 572 aof the first supercritical processing liquid supply unit 57 a, a flowrate adjustor 585 (e.g., a valve) interposed in the supply line 584, asupply line 586 that supplies the liquid R, which is regenerated fromthe liquid regenerator 583, to the reservoir 572 b of the secondsupercritical processing liquid supply unit 57 b, and a flow rateadjustor 587 (e.g., a valve) interposed in the supply line 586. Theliquid regenerator 583 produces the liquid R, for example, by coolingthe gas and/or the fluid supplied through the discharge line 581 and thedischarge line 541 of the discharge unit 54. For example, roomtemperature cooling water is used for the cooling. The liquid Rregenerated by the liquid regenerator 583 contains hydrofluoroolefin ofthe same kind as that contained in the supercritical processing liquid G(when the supercritical processing liquid G contains hydrofluoroolefinand an organic solvent, hydrofluoroolefin and an organic solvent of thesame kind as those contained in the supercritical processing liquid G).

The reservoir 572 a of the first supercritical processing liquid supplyunit 57 a is connected with a circulation pipe line 577 a in which apump 574 a, a concentration measuring unit 575 a, and a cooling unit 576a are interposed. When the supercritical processing liquid G stored inthe reservoir 572 a is circulated through the circulation pipe line 577a, the cooling unit 576 a cools the supercritical processing liquid G toa temperature (e.g., 10° C.) lower than the boiling point of thehydrofluoroolefin contained in the supercritical processing liquid GThis makes it difficult for the hydrofluoroolefin to evaporate from thesupercritical processing liquid G. Therefore, when the supercriticalprocessing liquid G is supplied to the substrate W2, collapse of theconcavo-convex pattern of the substrate W2 due to evaporation of thehydrofluoroolefin may be prevented. When the supercritical processingliquid G stored in the reservoir 572 a is circulated through thecirculation pipe line 577 a, the concentration measuring unit 575 ameasures the concentration of the hydrofluoroolefin in the supercriticalprocessing liquid G. When the supercritical processing liquid G containsan organic solvent (e.g., alcohol such as, for example, isopropylalcohol) in addition to the hydrofluoroolefin, the concentrationmeasuring unit 575 a also measures the concentration of the organicsolvent in the supercritical processing liquid G in addition to theconcentration of the hydrofluoroolefin in the supercritical processingliquid G. The concentration measuring method of the concentrationmeasuring unit 575 a is performed, for example, in a specific gravitymanner. For example, when the hydrofluoroolefin is1-chloro-3,3,3-trifluoropropene, its specific gravity is larger thanthat of water. When the organic solvent is isoproyl alcohol, itsspecific gravity is smaller than that of water. Therefore, theconcentrations of both may be measured by specific gravity.

The reservoir 572 b of the second supercritical processing liquid supplyunit 57 b is connected with a circulation pipe line 577 b in which apump 574 b, a concentration measuring unit 575 b, and a cooling unit 576b are interposed. When the supercritical processing liquid G stored inthe reservoir 572 b is circulated through the circulation pipe line 577b, the cooling unit 576 b cools the supercritical processing liquid G toa temperature (e.g., 10° C.) lower than the boiling point of thehydrofluoroolefin contained in the supercritical processing liquid GThis makes it difficult for the hydrofluoroolefin to evaporate from thesupercritical processing liquid G. Therefore, when the supercriticalprocessing liquid G is supplied to the substrate W2, collapse of theconcavo-convex pattern of the substrate W2 due to evaporation of thehydrofluoroolefin may be prevented. When the supercritical processingliquid G stored in the reservoir 572 b is circulated through thecirculation pipe line 577 b, the concentration measuring unit 575 bmeasures the concentration of the hydrofluoroolefin in the supercriticalprocessing liquid G. When the supercritical processing liquid G containsan organic solvent (e.g., alcohol such as, for example, isopropylalcohol) in addition to the hydrofluoroolefin, the concentrationmeasuring unit 575 b also measures the concentration of the organicsolvent in the supercritical processing liquid G in addition to theconcentration of the hydrofluoroolefin in the supercritical processingliquid G. The concentration measuring method of the concentrationmeasuring unit 575 b is performed, for example, in a specific gravitymanner.

The dry processing unit 5 includes a concentration adjusting unit 59that adjusts the concentration of the supercritical processing liquid Gstored in the reservoirs 572 a and 572 b. The concentration adjustingunit 59 adjusts the concentration of the supercritical processing liquidG stored in the reservoir 572 a by supplying a stock liquid H of thesupercritical processing liquid G from a reservoir 591 storing the stockliquid H to the reservoir 572 a through a supply pipe line 593 in whicha flow rate regulator 592 (e.g., a valve) is interposed. In addition,the concentration adjusting unit 59 adjusts the concentration of thesupercritical processing liquid G stored in the reservoir 572 b bysupplying the stock liquid H of the supercritical processing liquid Gfrom the reservoir 591 storing the stock liquid H to the reservoir 572 bthrough a supply pipe line 595 in which a flow rate regulator 594 (e.g.,a valve) is interposed. In the reservoirs 572 a and 572 b, the stockliquid H supplied from the concentration adjusting unit 59 and theliquid R supplied from the recycling unit 58 are mixed to prepare a newsupercritical processing liquid G. At this time, in order to adjust theconcentration of the supercritical processing liquid G stored in thereservoir 572 a to a predetermined concentration, the controller 3causes the flow rate adjustor 592 to adjust the flow rate of the stockliquid H and causes the flow rate adjustor 585 to adjust the flow rateof the liquid R, based on the hydrofluoroolefin concentration (thehydrofluoroolefin concentration and the organic solvent concentration inthe case where the supercritical processing liquid G contains an organicsolvent in addition to the hydrofluoroolefin) measured by theconcentration measuring unit 575 a. In addition, in order to adjust theconcentration of the supercritical processing liquid G stored in thereservoir 572 b to a predetermined concentration, the controller 3causes the flow rate adjustor 594 to adjust the flow rate of the stockliquid H and causes the flow rate adjustor 587 to adjust the flow rateof the liquid R, based on the hydrofluoroolefin concentration (thehydrofluoroolefin concentration and the organic solvent concentration inthe case where the supercritical processing liquid G contains an organicsolvent in addition to the hydrofluoroolefin) measured by theconcentration measuring unit 575 b.

<Configuration 02 of Dry Processing Unit>

Next, a specific configuration of the dry processing unit 5 will bedescribed with reference to FIGS. 4 and 5. FIG. 4 is a schematicperspective view illustrating a configuration of the dry processing unit5, and FIG. 5 is a schematic cross-sectional view illustrating theconfiguration of the dry processing unit 5.

The dry processing unit 5 performs a dry processing on the substrate W2which have been subjected to a substrate processing by the cleaningprocessing unit 4. The substrate W2 which have been subjected to asubstrate processing by the cleaning processing unit 4 is in a wet stateby a dry preventing liquid (e.g., a mixed liquid of the first drypreventing liquid 2L3 and the second dry preventing liquid 2L4) filledon the surface thereof. The substrate processing performed by the dryprocessing unit 5 is not particularly limited as long as the dryprocessing is included. Therefore, the processing performed by the dryprocessing unit 5 may include processings other than the dry processing.

The dry processing unit 5 includes a chamber 510, and performs thesubstrate processing including the dry processing in the chamber 510.

The chamber 510 includes an inner space 511 and an opening 512 leadingto the inner space 511. The inner space 511 and the opening 512 aredefined by the wall portion of the chamber 510. The chamber 510 isconfigured to seal the inner space 511 by sealing the opening 512. Theinner space 511 is a space capable of accommodating the substrate W2. Inthe exemplary embodiment, since the substrate W2 is accommodated in theinner space 511 in a state of being held by a substrate holding portion531, the inner space 511 is a space capable of accommodating thesubstrate holding unit 531 that holds the substrate W2. The size of theinner space 511 is, for example, about 200 to 10,000 cm³. Thecarry-in/out of the substrate W2 into/from the internal space 511 isperformed through the opening 512.

The chamber 510 includes a pressure-resistant container. Examples of thepressure-resistant container include a pressure-resistant container madeof a material having a high pressure resistance but a relatively lowthermal conductivity such as, for example, stainless steel, carbonsteel, titanium, Hastelloy (registered trademark), or Inconel(registered trademark). An inner container made of a material havinghigher thermal conductivity than that of the pressure-resistantcontainer (e.g., aluminum, copper, aluminum nitride, or silicon carbide)is provided inside the pressure-resistant container in a nestedstructure. The internal container may be heated. A thermal insulationlayer made of, for example, quartz or alumina is provided between thepressure-resistant container and the inner container, and only the innercontainer is heated, so that the thermal responsiveness of the chamber510 may be improved, and energy consumption may be reduced.

The dry processing unit 5 includes the substrate holding unit 531 thatholds the substrate W2. The substrate holding unit 531 is configured tohold the substrate W2 transversely in a state of being immersed in aliquid (e.g., liquid dialkyl ether G supplied from a first dialkyl ethersupply unit 57 a and/or a second dialkyl ether supply unit 57 b).

The dry processing unit 5 includes a cover member 532 provided in thesubstrate holding unit 531. The cover member 532 is configured to sealthe opening 512 of the chamber 510 when the substrate holding unit 531is accommodated in the inner space 511 of the chamber 510.

The dry processing unit 5 includes a transfer mechanism 56 that enablesthe substrate holding unit 531 to move between an external position ofthe chamber 510 (a position where the substrate W2 is delivered to andfrom the substrate holding unit 531) and an internal position of thechamber 510 (a position where the dry processing is performed on thesubstrate W2 held by the substrate holding unit 531). The transfermechanism 56 is a slide mechanism including a rail 561 extending in amovement direction of the substrate holding unit 531 and a slider 562with a built-in driving mechanism that travels on the rail 561, and isprovided on both sides of the substrate holding unit 531. The slider 562is connected to the cover member 532. Therefore, as the slider 562 movesalong the rail 561, the cover member 532 and the substrate holding unit531 connected to the cover member 532 also move along the rail 561.Specifically, when the slider 562 moves to one end portion of the rail561, the substrate holding unit 531 may move to the external position ofthe chamber 510. When the slider 562 moves to the other end portion ofthe rail 561, the substrate holding unit 531 may move to the internalposition of the chamber 10.

The dry processing unit 5 includes a heating unit 52 that heats theinside of the chamber 510. The heating unit 52 is a heater made of, forexample, a heating resistor, and is provided in the wall portion of thechamber 510. The heating unit 52 may heat the substrate W2 in chamber510 through heating of the inside of the chamber 510. The heating unit52 may change the heat generation amount by a power supplied from apower supply unit 521, and may increase the temperature in the chamber510 according to a predetermined heating schedule, based on, forexample, a temperature detection result acquired from a temperaturedetection unit 522 or a pressure detection result of a pressuredetection unit 513.

The dry processing unit 5 includes a first dialkyl ether supply unit 57a that supplies a liquid dialkyl ether G represented by R¹—O—R² (whereinR¹ and R² represent the same or different alkyl groups) to the substrateW2 held by the substrate holding unit 531 when the substrate holdingunit 531 is positioned at the external position of the chamber 510, anda second dialkyl ether supply unit 57 b that supplies the liquid dialkylether G to the substrate W2 held by the substrate holding unit 531 whenthe substrate holding unit 531 is positioned at the inner position ofthe chamber 510. The liquid dialkyl ether G supplied by the firstdialkyl ether supply unit 57 a and the liquid dialkyl ether G suppliedby the second dialkyl ether supply unit 57 b may be the same as ordifferent from each other. However, in the exemplary embodiment, theyare the same.

The dry processing unit 5 may include only one of the first dialkylether supply unit 57 a and the second dialkyl ether supply unit 57 b. Inthe exemplary embodiment in which the dry processing unit 5 includesboth of the first dialkyl ether supply unit 57 a and the second dialkylether supply unit 57 b, the position of the substrate holding unit 531when the liquid dialkyl ether G is supplied to the substrate W2 may beeither the external position of the chamber 510 or the internal positionof the chamber 510. However, in an exemplary embodiment in which the dryprocessing unit includes the first dialkyl ether supply unit 57 a only,the position of the substrate holding unit 531 when the liquid dialkylether G is supplied to the substrate W2 is the external position of thechamber 510. In an exemplary embodiment in which the dry processing unit5 includes the second dialkyl ether supply unit 57 b only, the positionof the substrate holding unit 531 when the liquid dialkyl ether G issupplied to the substrate W2 is the internal position of the chamber510.

The first dialkyl ether supply unit 57 a includes a dialkyl ether supplypipe 571 a that ejects the liquid dialkyl ether G to the substrate W2held by the substrate holding unit 531 when the substrate holding unit531 is positioned at the external position of the chamber 510, and adialkyl ether source 572 a that supplies the liquid dialkyl ether G tothe dialkyl ether supply pipe 571 a. The liquid dialkyl ether G isstored in a tank provided in the dialkyl ether source 572 a. The liquiddialkyl ether G is supplied to the dialkyl ether supply pipe 571 a fromthe dialkyl ether source 572 a through a flow rate adjustor 573 a (e.g.,a valve).

The second dialkyl ether supply unit 57 b includes a dialkyl ethersupply pipe 571 b that ejects the liquid dialkyl ether G to thesubstrate W2 held by the substrate holding unit 531 when the substrateholding unit 531 is positioned at the external position of the chamber510, and a dialkyl ether source 572 b that supplies the liquid dialkylether G to the dialkyl ether supply pipe 571 b. The liquid dialkyl etherG is stored in a tank provided in the dialkyl ether source 572 b. Theliquid dialkyl ether G is supplied to the dialkyl ether supply pipe 571b from the dialkyl ether source 572 b through a flow rate adjustor 573 b(e.g., a valve).

In the exemplary embodiment, the second dialkyl ether supply unit 57 bejects the liquid dialkyl ether G directly to the substrate W2 held bythe substrate holding unit 531 when the substrate holding unit 531 ispositioned at the internal position of the chamber 510, but the supplyembodiment of the liquid dialkyl ether G by the second dialkyl ethersupply unit 57 b is not limited to the exemplary embodiment. Forexample, when the substrate holding unit 531 is positioned at theinternal position of the chamber 510, the second dialkyl ether supplyunit 57 b may not eject the liquid dialkyl ether G directly to thesubstrate W2 held by the substrate holding unit 531, but eject theliquid dialkyl ether G to the bottom portion of the chamber 510 or thebottom portion of the substrate holding unit 531 that supports thesubstrate W2. Further, in the exemplary embodiment, the dialkyl ether Gsupplied by the second dialkyl ether supply unit 57 b is liquid, but thephase of the dialkyl ether G supplied from the second dialkyl ethersupply unit 57 b is not limited to that in the exemplary embodiment. Forexample, the dialkyl ether G supplied from the second dialkyl ethersupply unit 57 b may be in the form of a supercritical fluid or asubcritical fluid.

Examples of the alkyl group represented by R¹ or R² include a linear orbranched alkyl group having 1 to 8 carbon atoms such as, for example, amethyl group, an ethyl group, an n-propyl group, an isopropyl group, ann-butyl group, an isobutyl group, a s-butyl group, a t-butyl group, apentyl group, a hexyl group, a heptyl group, and an octyl group. Thecarbon number of the alkyl group represented by R¹ or R² is notparticularly limited, but is preferably 1 to 5, and more preferably 1 to4.

The liquid dialkyl ether G is a liquid at normal temperature andpressure. The liquid dialkyl ether G is miscible with the first drypreventing liquid 2L3 and the second dry preventing liquid 2L4, and mayhave a boiling point of 50° C. or more, a critical temperature of 250°C. or less, and a critical pressure of 10 MPa or less. Examples of thedialkyl ether that satisfies these conditions include methyl tert-butylether (MTBE) and diisopropyl ether (DIPE). MTBE is miscible with IPA andPGMEA, and has a boiling point of 55° C., a critical temperature of 224°C., and a critical pressure of 3.4 MPa. DIPE is miscible with IPA andPGMEA, and has a boiling point of 69° C., a critical temperature of 227°C., and a critical pressure of 2.9 MPa. MTBE is desirable in that itslow global warming potential coefficient (GWP=1) does not requirerecovery of the exhaust gas and the waste liquid such as PFC.

The dry processing unit 5 includes a discharge unit 54 that dischargesthe fluid in the chamber 510. The discharge unit 54 includes a dischargeline 541 that discharges the fluid in the chamber 510, and a flow rateadjustor 542 (e.g., a valve) interposed in the discharge line 541. Theflow rate adjustor 542 (e.g., a valve) adjusts the discharge amount ofthe fluid such that the inside of the chamber 510 is adjusted to apredetermined pressure.

[First Substrate Processing Method]

Hereinafter, descriptions will be made on a substrate processing methodperformed by the substrate processing apparatus 1. The substrateprocessing method performed by the substrate processing apparatus 1includes a cleaning step of cleaning the substrate W1 and a dry step ofdrying the substrate W2 after the cleaning step. The cleaning step isperformed by the cleaning processing unit 4, and the dry step isperformed by the dry processing unit 5. The operation of the cleaningprocessing unit 4 and the operation of the dry processing unit 5 arecontrolled by the controller 3.

<Step of Carrying Substrate into Cleaning Processing Unit>

First, the substrate W1 is carried into the cleaning processing unit 4.At this time, the conveyance mechanism 213 takes out the substrate W1from the carrier C placed on the placing unit 211, and places thetaken-out substrate W1 on the delivery section 214. The conveyancemechanism 222 takes out the substrate W1 placed on the delivery unit214, and carries the taken-out substrate W1 into the cleaning processingunit 4.

The substrate processing apparatus 1 holds the substrate W1, which hasbeen carried into the cleaning processing unit 4, by the holding unit42. At this time, the substrate holding unit 42 horizontally holds thesubstrate W1 on the turntable 422 in a state where the outer edgeportion of the substrate W1 is supported by the chuck 423. The drivingunit 424 rotates the substrate W1 held by the substrate holding unit 42at a predetermined speed. The controller 3 controls the operation of thedriving unit 424 to control, for example, the rotation timing androtation speed of the substrate W1.

<Cleaning Step>

Subsequently, a cleaning step by the cleaning processing unit 4 isperformed on the substrate W1 held by the substrate holding unit 42.

In the cleaning step, the nozzle 1431 a of the cleaning liquid supplyunit 1043 a is positioned above the center of the substrate W1 while thesubstrate W1 held by the substrate holding unit 42 is rotated at apredetermined speed, and the cleaning liquid 1L1 is supplied from thenozzle 1431 a to the substrate W1. At this time, the controller 3controls the operation of the cleaning liquid supply unit 1043 a tocontrol the supply timing, the supply time, and the supply amount of thecleaning liquid 1L1. The cleaning liquid 1L1 supplied to the substrateW1 is diffused over the substrate W1 by the centrifugal forceaccompanying the rotation of the substrate W1. As a result, depositsattached to the substrate W1 are removed from the substrate W1.

<Rinse Step>

After the cleaning step, a rinse step by the cleaning processing unit 4is performed on the substrate W1 held by the substrate holding unit 42.

In the rinse step, the nozzle 1431 b of the rinse liquid supply unit1043 b is positioned above the center of the substrate W1 while thesubstrate W1 held by the substrate holding unit 42 is rotated at apredetermined speed, and the rinse liquid 1L2 is supplied from thenozzle 1431 b to the substrate W1. At this time, the controller 3controls the operation of the rinse liquid supply unit 1043 b to controlthe supply timing, the supply time, and the supply amount of the rinseliquid 1L2. The rinse liquid 1L2 supplied to the substrate W1 isdiffused over the substrate W1 by the centrifugal force accompanying therotation of the substrate W1. As a result, the cleaning liquid 1L1remaining on the substrate W1 is washed out.

<Dry Preventing Liquid Supply Step>

After the rinse step, a dry preventing liquid supply step by thecleaning processing unit 4 is performed on the substrate W1 held by thesubstrate holding unit 42.

In the dry preventing liquid supply step, the nozzle 1431 c of the drypreventing liquid supply unit 1043 c is positioned above the center ofthe substrate W1 while the substrate W1 held by the substrate holdingunit 42 is rotated at a predetermined speed, or while the substrate W1held by the substrate holding unit 42 is maintained in a stopped state,and a dry preventing liquid 1L3 is supplied from the nozzle 1431 c tothe substrate W1. At this time, the controller 3 controls the operationof the dry preventing liquid supply unit 1043 c to control the supplytiming, the supply time, and the supply amount of the dry preventingliquid 1L3. In the dry preventing supply step, the rinse liquid 1L2remaining on the substrate W1 is replaced with the dry preventing liquid1L3. The dry preventing liquid 1L3 filled on the substrate W1 functionsas a dry preventing liquid to suppress occurrence of pattern collapsedue to the drying of the surface of the substrate during the conveyanceof the substrate from the cleaning processing unit 4 to the dryprocessing unit 5 and the carry of the substrate into the dry processingunit 5.

<Step of Carrying Substrate into Dry Processing Unit>

The substrate W2 which have been subjected to a substrate processing bythe cleaning processing unit 4 is in a wet state by the dry preventingliquid 1L3 filled on the surface thereof. While maintaining the wetstate, the substrate W2 is carried out from the cleaning processing unit4 and carried into the dry processing unit 5. At this time, theconveyance mechanism 222 takes out the substrate W2 from the cleaningprocessing unit 4, and carries the taken-out substrate W2 into the dryprocessing chamber 500 in the dry processing unit 5. The conveyancemechanism 222 may have, for example, a cooling mechanism or a covermechanism to suppress vaporization (evaporation) of the dry preventingliquid 1L3 filled on the surface of the substrate W2 from the substrateW2 during the conveyance.

The substrate W2 carried into the dry processing chamber 500 of the dryprocessing unit 5 is held by the substrate holding unit 531 waiting atthe external position of the supercritical processing chamber 510. Atthis time, the power supply unit 521 is OFF, and the internal space 511of the supercritical processing chamber 510 is at a temperature equal toor lower than the critical temperature of the supercritical processingliquid G and atmospheric pressure. An inert gas (e.g., N₂ gas) is purgedinto the internal space 511 of the supercritical processing chamber 510to keep the inside of the supercritical processing chamber 510 in a lowoxygen atmosphere, and heating in the supercritical processing chamber510 is started by the heating unit 52. Then, it is desirable that acombustible gas (e.g., IPA) is not brought into contact with arelatively high concentration of oxygen under a high temperatureatmosphere.

<Supercritical Processing Liquid Supply Step>

When the substrate holding unit 531 holding the substrate W2 ispositioned at the external position of the supercritical processingchamber 510 (i.e., before the substrate W2 is accommodated in thesupercritical processing chamber 510), the first supercriticalprocessing liquid supply unit 57 a supplies the supercritical processingliquid G to the substrate W2 held by the substrate holding unit 531. Thefirst supercritical processing liquid supply unit 57 a supplies thesupercritical processing liquid G, for example, until the substrate W2held by the substrate holding unit 531 is immersed in the supercriticalprocessing liquid G, or until the supercritical processing liquid G isfilled on the surface of the substrate W2 held by the substrate holdingunit 531.

<Dry Step>

After the supercritical processing liquid G is supplied to the substrateW2, the substrate holding unit 531 is moved from the external positionof the supercritical processing chamber 510 to the internal position ofthe supercritical processing chamber 510 through the opening 512 of thesupercritical processing chamber 510 such that the substrate W2 isaccommodated in the supercritical processing chamber 510 while beingheld by the substrate holding unit 531. When the substrate holding unit531 is moved to the internal position of the supercritical processingchamber 510, the opening 512 is sealed by the cover member 532, so thatthe inside of the supercritical processing chamber 510 is closed.

When the substrate holding unit 531 holding the substrate W2 ispositioned at the internal position of the supercritical processingchamber 510, the second supercritical processing liquid supply unit 57 bmay supply the supercritical processing liquid G to the substrate W2held by the substrate holding unit 531 as necessary (for example, inorder to compensate for the volatilization reduction of thesupercritical processing liquid G supplied from the first supercriticalprocessing liquid supply unit 57 a).

After the substrate holding unit 531 holding the substrate W2 isaccommodated in the supercritical processing chamber 510 (in the casewhere the supercritical processing liquid G is supplied to the substrateW2 held by the substrate holding unit 531, by the second supercriticalprocessing liquid supply unit 57 b, after the supply thereof), theinside of the supercritical processing chamber 510 is heated by theheating unit 52. Specifically, power supply from the power supply unit521 to the heating unit 52 is started, and the inside of thesupercritical processing chamber 510 is heated by the heating unit 52.At this time, since the inside of the supercritical processing chamber510 is pressurized by the vapor pressure of the supercritical processingliquid G, the supercritical processing liquid G is heated along thevapor pressure curve while being maintained in the liquid state.Further, a part of the supercritical processing liquid G is vaporized sothat the pressure inside the supercritical processing chamber 510 isincreased.

When the temperature-pressure state of the supercritical processingchamber 510 comes close to the critical point (critical temperature Tcand critical pressure Pc) of the supercritical processing liquid G, thesupercritical processing liquid G is changed into a subcritical fluid.When the temperature-pressure state of the supercritical processingchamber 510 exceeds the critical point (critical temperature Tc andcritical pressure Pc) of the supercritical processing liquid G, thesupercritical processing liquid G is changed into a supercritical fluid.In practice, the atmosphere in the supercritical processing chamber 510is in a state where the dry preventing liquid 1L3 is mixed with a fluidsuch as, for example, air flowing from the outside. However, when thesupercritical processing liquid G is in a supercritical state orsubcritical state, the liquid is dissolved so that no liquid surface ispresent inside the pattern. Therefore, when the critical processingliquid G comes into the supercritical state or subcritical state, theliquid on the surface may be removed from the substrate W2 withoutcausing pattern collapse.

Thus, after the lapse of time sufficient for the supercriticalprocessing liquid G in the supercritical processing chamber 510 to bechanged into the supercritical fluid or subcritical fluid, the flow rateadjustor 542 (e.g., a valve) of the discharge line 541 is opened todischarge the fluid in the supercritical processing chamber 510. Whenthe pressure inside the supercritical processing chamber 510 becomesequal to or lower than the critical pressure of the supercriticalprocessing liquid G, the supercritical processing liquid G undergoes aphase change from the supercritical or subcritical fluid to a gas. Atthis time, when the temperature of the supercritical processing chamber510 is adjusted to a temperature (e.g., 250° C.) equal to or higher thanthe boiling point of the hydrofluoroolefin, it is possible to dischargethe fluid inside the supercritical processing chamber 510 from thesupercritical processing chamber 510 in a state of a supercritical orsubcritical fluid or a gas while suppressing reliquefaction of thehydrofluoroolefin. As a result, in the supercritical processing chamber510 which is depressurized to the atmospheric pressure, it is possibleto obtain a dried substrate W3 from which the liquid has been removedfrom the surface thereof.

<Step of Carrying Substrate Out from Dry Processing Unit>

After the dry step, the substrate W3 is carried out from the dryprocessing unit 5. At this time, the conveyance mechanism 222 takes outthe substrate W3 from the dry processing unit 5 and places the taken-outsubstrate W3 on the delivery unit 214. The conveyance mechanism 213takes out the substrate W3 placed on the delivery unit 214 and andstores the substrate W3 in the carrier C of the placing unit 211.

<Liquid Regeneration Step>

When the substrate holding unit 531 holding the substrate W2 ispositioned at the external position of the supercritical processingchamber 510 (i.e., before the substrate W2 is accommodated in thesupercritical processing chamber 510), the fluid in the dry processingchamber 500 is discharged through the discharge line 581 of therecycling unit 58 when or after the first supercritical processingliquid supply unit 57 a supplies the supercritical processing liquid Gto the substrate W2 held by the substrate holding unit 531. Therefore,when the substrate holding unit 531 is positioned at the externalposition of the supercritical processing chamber 510, the gas vaporizedfrom the supercritical processing liquid G supplied to the substrate W2held by the substrate holding unit 531 is supplied to the liquidregenerator 583. The amount of the gas to be supplied to the liquidregenerator 583 is adjusted by the flow rate adjustor 582 (e.g., avalve) interposed in the discharge line 581. The liquid regenerator 583regenerates a liquid (R) from the supplied gas. The regenerated liquid(R) is supplied to the reservoir(s) 572 a and/or 572 b together with theliquid (R) regenerated from the fluid discharged from the discharge unit54.

The fluid discharged by the discharge unit 54 is supplied to the liquidregenerator 583 of the recycling unit 58 through the discharge line 541.The amount of the gas to be supplied to the liquid regenerator 583 isadjusted by the flow rate adjustor 542 (e.g., a valve) interposed in thedischarge line 541. The liquid regenerator 583 regenerates a liquid (R)from the supplied fluid. The regenerated liquid (R) is supplied to thereservoir(s) 572 a and/or 572 b together with the liquid (R) regeneratedfrom the gas discharged from the dry processing chamber 500.

<Supercritical Processing Liquid Concentration Adjustment Step>

After the regenerated liquid (R) is supplied to the reservoir(s) 572 aand/or 572 b, the concentration of the supercritical processing liquid Gstored in the reservoir(s) 572 a and/or 572 b is adjusted by theconcentration adjusting unit 59. Specifically the concentrationadjusting unit 59 adjusts the concentration of the supercriticalprocessing liquid G stored in the reservoir 572 a by supplying a stockliquid H of the supercritical processing liquid G from a reservoir 591storing the stock liquid H to the reservoir 572 a through a supply pipeline 593 in which a flow rate regulator 592 (e.g., a valve) isinterposed. In addition, the concentration adjusting unit 59 adjusts theconcentration of the supercritical processing liquid G stored in thereservoir 572 b by supplying the stock liquid H of the supercriticalprocessing liquid G from the reservoir 591 storing the stock liquid H tothe reservoir 572 b through a supply pipe line 595 in which a flow rateregulator 594 (e.g., a valve) is interposed. In the reservoirs 572 a and572 b, the stock liquid H supplied from the concentration adjusting unit59 and the liquid R supplied from the recycling unit 58 are mixed toprepare a new supercritical processing liquid G. At this time, in orderto adjust the concentration of the supercritical processing liquid Gstored in the reservoir 572 a to a predetermined concentration, thecontroller 3 causes the flow rate adjustor 592 to adjust the flow rateof the stock liquid H and causes the flow rate adjustor 585 to adjustthe flow rate of the liquid R, based on the hydrofluoroolefinconcentration (the hydrofluoroolefin concentration and the organicsolvent concentration in the case where the supercritical processingliquid G contains an organic solvent in addition to thehydrofluoroolefin) measured by the concentration measuring unit 575 a.In addition, in order to adjust the concentration of the supercriticalprocessing liquid G stored in the reservoir 572 b to a predeterminedconcentration, the controller 3 causes the flow rate adjustor 594 toadjust the flow rate of the stock liquid H and causes the flow rateadjustor 587 to adjust the flow rate of the liquid R, based on thehydrofluoroolefin concentration (the hydrofluoroolefin concentration andthe organic solvent concentration in the case where the supercriticalprocessing liquid G contains an organic solvent in addition to thehydrofluoroolefin) measured by the concentration measuring unit 575 b.

[Second Substrate Processing Method]

Hereinafter, descriptions will be made on a substrate processing methodperformed by the substrate processing apparatus 1. The substrateprocessing method performed by the substrate processing apparatus 1includes a cleaning step of cleaning the substrate W1 and a dry step ofdrying the substrate W2 after the cleaning step. The cleaning step isperformed by the cleaning processing unit 4, and the dry step isperformed by the dry processing unit 5. The operation of the cleaningprocessing unit 4 and the operation of the dry processing unit 5 arecontrolled by the controller 3.

<Step of Carrying Substrate into Cleaning Processing Unit>

First, the substrate W1 is carried into the cleaning processing unit 4.At this time, the conveyance mechanism 213 takes out the substrate W1from the carrier C placed on the placing unit 211, and places thetaken-out substrate W1 on the delivery section 214. The conveyancemechanism 222 takes out the substrate W1 placed on the delivery unit214, and carries the taken-out substrate W1 into the cleaning processingunit 4.

The substrate processing apparatus 1 holds the substrate W1, which hasbeen carried into the cleaning processing unit 4, by the holding unit42. At this time, the substrate holding unit 42 horizontally holds thesubstrate W1 on the turntable 422 in a state where the outer edgeportion of the substrate W1 is supported by the chuck 423. The drivingunit 424 rotates the substrate W1 held by the substrate holding unit 42at a predetermined speed. The controller 3 controls the operation of thedriving unit 424 to control, for example, the rotation timing androtation speed of the substrate W1.

<Cleaning Step>

Subsequently, a cleaning step by the cleaning processing unit 4 isperformed on the substrate W1 held by the substrate holding unit 42.

In the cleaning step, the nozzle 2431 a of the cleaning liquid supplyunit 2043 a is positioned above the center of the substrate W1 while thesubstrate W1 held by the substrate holding unit 42 is rotated at apredetermined speed, and the cleaning liquid 2L1 is supplied from thenozzle 2431 a to the substrate W1. At this time, the controller 3controls the operation of the cleaning liquid supply unit 2043 a tocontrol the supply timing, the supply time, and the supply amount of thecleaning liquid 2L1. The cleaning liquid 2L1 supplied to the substrateW1 is diffused over the substrate W1 by the centrifugal forceaccompanying the rotation of the substrate W1. As a result, depositsattached to the substrate W1 are removed from the substrate W1.

<Rinse Step>

After the cleaning step, a rinse step by the cleaning processing unit 4is performed on the substrate W1 held by the substrate holding unit 42.

In the rinse step, the nozzle 2431 b of the rinse liquid supply unit2043 b is positioned above the center of the substrate W1 while thesubstrate W1 held by the substrate holding unit 42 is rotated at apredetermined speed, and the rinse liquid 2L2 is supplied from thenozzle 2431 b to the substrate W1. At this time, the controller 3controls the operation of the rinse liquid supply unit 2043 b to controlthe supply timing, the supply time, and the supply amount of the rinseliquid 2L2. The rinse liquid 2L2 supplied to the substrate W1 isdiffused over the substrate W1 by the centrifugal force accompanying therotation of the substrate W1. As a result, the cleaning liquid 2L1remaining on the substrate W1 is washed out.

<First Dry Preventing Liquid Supply Step>

After the rinse step, a first dry preventing liquid supply step by thecleaning processing unit 4 is performed on the substrate W1 held by thesubstrate holding unit 42.

In the first dry preventing liquid supply step, the nozzle 2431 c of thefirst dry preventing liquid supply unit 2043 c is positioned above thecenter of the substrate W1 while the substrate W1 held by the substrateholding unit 42 is rotated at a predetermined speed, or while thesubstrate W1 held by the substrate holding unit 42 is maintained in astopped state, and a first dry preventing liquid 2L3 is supplied fromthe nozzle 2431 c to the substrate W1. At this time, the controller 3controls the operation of the first dry preventing liquid supply unit2043 c to control the supply timing, the supply time, and the supplyamount of the first dry preventing liquid 2L3. In the first drypreventing supply step, the rinse liquid 2L2 remaining on the substrateW1 is replaced with the first dry preventing liquid 2L3. The first drypreventing liquid 2L3 filled on the substrate W1 functions as a drypreventing liquid to suppress occurrence of pattern collapse due to thedrying of the surface of the substrate during the conveyance of thesubstrate from the cleaning processing unit 4 to the dry processing unit5 and the carry of the substrate into the dry processing unit 5.

<Second Dry Preventing Liquid Supply Step>

After the first dry preventing liquid supply step, a second drypreventing liquid supply step by the cleaning processing unit 4 isperformed on the substrate W1 held by the substrate holding unit 42.

In the second dry preventing liquid supply step, the nozzle 2431 d ofthe second dry preventing liquid supply unit 2043 d is positioned abovethe center of the substrate W1 while the substrate W1 held by thesubstrate holding unit 42 is rotated at a predetermined speed, or whilethe substrate W1 held by the substrate holding unit 42 is maintained ina stopped state, and a second dry preventing liquid 2L4 is supplied fromthe nozzle 2431 d to the substrate W1. At this time, the controller 3controls the operation of the second dry preventing liquid supply unit2043 d to control the supply timing, the supply time, and the supplyamount of the second dry preventing liquid 2L4. In the second drypreventing supply step, a part of the first dry preventing liquid 2L3remaining on the substrate W1 is replaced with the second dry preventingliquid 2L4. Accordingly, the surface of the substrate W1 is in a stateof being filled with a mixed liquid of the first dry preventing liquid2L3 and the second dry preventing liquid 2L4.

The second dry preventing liquid 2L4 filled on the substrate W1functions as a dry preventing liquid to suppress occurrence of patterncollapse due to the drying of the surface of the substrate during theconveyance of the substrate from the cleaning processing unit 4 to thedry processing unit 5 and the carry of the substrate into the dryprocessing unit 5. In the exemplary embodiment, a part of the first drypreventing liquid 2L3 filled on the surface of the substrate is replacedwith the second dry preventing liquid 2L4. However, since the first drypreventing liquid 2L3 alone is able to function as a dry preventingliquid, a part of the first dry preventing liquid 2L3 filled on thesurface of the substrate may not be replaced with the second drypreventing liquid 2L4. When IPA is used as the first dry preventingliquid 2L3, PGMEA may be used as the second dry preventing liquid 2L4,so that a part of the IPA filled on the surface of the substrate isreplaced with the PGMEA. Accordingly, the drying of the surface of thesubstrate may be suppressed as compared with a case of IPA alone,thereby enhancing the function as a dry preventing liquid. Further,unlike IPA, PGMEA does not have OH groups. Thus, PGMEA does not form aLewis acid or a complex with a metal such as, for example, tungsten (W),and does not cause any damage such as W whisker. From these points, apart of the IPA filled on the surface of the substrate may be replacedwith PGMEA.

<Step of Carrying Substrate into Dry Processing Unit>

The substrate W2 which have been subjected to a substrate processing bythe cleaning processing unit 4 is in a wet state by the dry preventingliquid (e.g., a mixed liquid of the first dry preventing liquid 2L3 andthe second dry preventing liquid 2L4) filled on the surface thereof.While maintaining the wet state, the substrate W2 is carried out fromthe cleaning processing unit 4 and carried into the dry processing unit5. At this time, the conveyance mechanism 222 takes out the substrate W2from the cleaning processing unit 4, and carries the taken-out substrateW2 into the dry processing unit 5. The conveyance mechanism 222 mayhave, for example, a cooling mechanism or a cover mechanism to suppressvaporization (evaporation) of the dry preventing liquid (e.g., a mixedliquid of the first dry preventing liquid 2L3 and the second drypreventing liquid 2L4) filled on the surface of the substrate W2 fromthe substrate W2 during the conveyance.

The substrate W2 carried into the dry processing unit 5 is held by thesubstrate holding unit 531 waiting at the external position of thechamber 510. At this time, the power supply unit 521 is OFF, and theinternal space 511 of the supercritical processing chamber 510 is at atemperature equal to or lower than the critical temperature of thedialkyl ether G and atmospheric pressure. An inert gas (e.g., N₂ gas) ispurged into the internal space 511 of the chamber 510 to keep the insideof the chamber 510 in a low oxygen atmosphere, and heating in thechamber 510 is started by the heating unit 52. Then, it is desirablethat a combustible gas (e.g., IPA or MTBE) is not brought into contactwith a relatively high concentration of oxygen under a high temperatureatmosphere.

<Dialkyl Ether Supply Step>

When the substrate holding unit 531 holding the substrate W2 ispositioned at the external position of the chamber 510, a first dialkylether supply unit 57 a supplies a liquid dialkyl ether G to thesubstrate W2 held by the substrate holding unit 531. The first dialkylether supply unit 57 a supplies the liquid dialkyl ether G, for example,until the substrate W2 held by the substrate holding unit 531 isimmersed in the liquid dialkyl ether G, or until the liquid dialkylether G is filled on the surface of the substrate W2 held by thesubstrate holding unit 531.

<Dry Step>

After the dialkyl ether G is supplied to the substrate W2, the substrateholding unit 531 is moved from the external position of the chamber 510to the internal position of the chamber 510 through the opening 512 ofthe chamber 510 such that the substrate W2 is accommodated in thechamber 510 while being held by the substrate holding unit 531. When thesubstrate holding unit 531 is moved to the internal position of thechamber 510, the opening 512 is sealed by the cover member 532, so thatthe inside of the chamber 510 is closed.

When the substrate holding unit 531 holding the substrate W2 ispositioned at the internal position of the chamber 510, a second dialkylether supply unit 57 b may supply the liquid dialkyl ether G to thesubstrate W2 held by the substrate holding unit 531 as necessary (forexample, in order to compensate for the volatilization reduction of thedialkyl ether G supplied from the first dialkyl ether supply unit 57 a).

After the substrate holding unit 531 holding the substrate W2 isaccommodated in the chamber 510 (in the case where the liquid dialkylether G is supplied to the substrate W2 held by the substrate holdingunit 531, by the second dialkyl ether supply unit 57 b, after the supplythereof), the inside of the chamber 510 is heated by the heating unit52. Specifically, power supply from the power supply unit 521 to theheating unit 52 is started, and the inside of the chamber 510 is heatedby the heating unit 52. At this time, since the inside of the chamber510 is pressurized by the vapor pressure of the dialkyl ether G, thedialkyl ether G on the substrate W2 is heated along the vapor pressurecurve while being maintained in the liquid state. Further, a part of thedialkyl ether G is vaporized so that the pressure inside the chamber 510is increased.

When the temperature-pressure state of the chamber 510 comes close tothe critical point (critical temperature Tc and critical pressure Pc) ofthe dialkyl ether G, the dialkyl ether G is changed into a subcriticalfluid. When the temperature-pressure state of the chamber 510 exceedsthe critical point (critical temperature Tc and critical pressure Pc) ofthe dialkyl ether G, the dialkyl ether G is changed into a supercriticalfluid. In practice, the atmosphere in the supercritical processingchamber 510 is in a state where the first dry preventing liquid 2L3, thesecond dry preventing liquid 2L4, and a fluid such as, for example, airflowing from the outside are mixed. However, when the dialkyl ether G isin a supercritical state or subcritical state, the liquid is dissolvedso that no liquid surface is present inside the pattern. Therefore, whenthe dialkyl ether G comes into the supercritical state or subcriticalstate, the liquid on the surface may be removed from the substrate W2without causing pattern collapse.

Thus, after the lapse of time sufficient for the dialkyl ether G in thechamber 510 to be changed into the supercritical fluid or subcriticalfluid, the flow rate adjustor 542 (e.g., a valve) of the discharge line541 is opened to discharge the fluid in the supercritical processingchamber 510. When the pressure inside the chamber 510 becomes equal toor lower than the critical pressure of the dialkyl ether G, the dialkylether G undergoes a phase change from the supercritical or subcriticalfluid to a gas. At this time, when the temperature of the chamber 510 isadjusted to a temperature (e.g., 250° C.) equal to or higher than theboiling point of the hydrofluoroolefin, it is possible to discharge thefluid inside the chamber 510 from the chamber 510 in a state of asupercritical or subcritical fluid or a gas while suppressingreliquefaction of the dialkyl ether G As a result, in the chamber 510which is depressurized to the atmospheric pressure, it is possible toobtain a dried substrate W3 from which the liquid has been removed fromthe surface thereof.

In the exemplary embodiment, the dialkyl ether G is used as a liquidwhich becomes a source of the supercritical or subcritical fluid. Sincethe dialkyl ether G does not have an OH group, the dialkyl ether G doesnot form a Lewis acid or a complex with a metal such as, for example,tungsten (W), and does not cause any damage such as W whisker. Inaddition, since the dialkyl ether G does not contain fluorine, nofluorine may be generated under a high temperature and high pressurecondition which is used for changing a liquid into a supercritical fluidor a subcritical fluid. Thus, no damage is caused by fluorine.

<Step of Carrying Substrate Out from Dry Processing Unit>

After the dry step, the substrate W3 is carried out from the dryprocessing unit 5. At this time, the conveyance mechanism 222 takes outthe substrate W3 from the dry processing unit 5 and places the taken-outsubstrate W3 on the delivery unit 214. The conveyance mechanism 213takes out the substrate W3 placed on the delivery unit 214 and andstores the substrate W3 in the carrier C of the placing unit 211.

EXAMPLE Reference Example 1

A silicon wafer having a concavo-convex pattern composed of convexportions and concave portions formed on its surface was sequentiallyimmersed in deionized water (DIW) and isopropyl alcohol (IPA), and thentaken out. The taken-out silicon wafer was immersed in about 2.5 mL ofIPA in a test tube. Then, about 23 mL of perfluorocarbon (Fluorinert(registered trademark) FC-72 manufactured by Sumitomo 3M Limited) wasadded to the test tube. After the addition of FC-72, the test tube wasintroduced into the chamber, and a supercritical processing wasperformed in the chamber. The supercritical processing was performed bymaintaining the temperature and pressure inside the chamber at 230° C.and 2.8 MPa for 20 minutes, respectively. Incidentally, 230° C. is atemperature higher than the critical temperature (175° C.) of FC-72, and2.8 MPa is a pressure higher less than the critical pressure (1.9 MPa)of FC-72. After the supercritical processing, the inside of the chamberwas depressurized, and the silicon wafer was taken out from the testtube.

After the supercritical processing, the concavo-convex pattern on thesurface of the silicon wafer was observed by a scanning electronmicroscope (SEM), and conditions were set such that collapse of theconcavo-convex pattern was not observed. As a result, the obtainedconditions are as follows.

-   -   The liquid in the chamber reaches its critical temperature.    -   The entire liquid in the chamber changes to a supercritical        fluid, subcritical fluid, or gas.    -   After supercritical processing, the pressure inside the chamber        is reduced at a low speed (2 MPa/min).

The following examples and comparative examples were carried outaccording to the conditions obtained in Reference Example 1.

Reference Example 2

A silicon wafer having a concavo-convex pattern composed of convexportions and concave portions formed on its surface was sequentiallyimmersed in deionized water (DIW) and isopropyl alcohol (IPA), and thentaken out. The taken-out silicon wafer was immersed in about 2.5 mL ofIPA in a test tube. Then, about 23 mL of perfluorocarbon (Fluorinert(registered trademark) FC-72 manufactured by Sumitomo 3M Limited) wasadded to the test tube. After the addition of FC-72, the test tube wasintroduced into the chamber, and a supercritical processing wasperformed in the chamber. The supercritical processing was performed bymaintaining the temperature and pressure inside the chamber at 230° C.and 2.8 MPa for 20 minutes, respectively. Incidentally, 230° C. is atemperature higher than the critical temperature (175° C.) of FC-72, and2.8 MPa is a pressure higher less than the critical pressure (1.9 MPa)of FC-72. After the supercritical processing, the inside of the chamberwas depressurized, and the silicon wafer was taken out from the testtube.

After the supercritical processing, the concavo-convex pattern on thesurface of the silicon wafer was observed by a scanning electronmicroscope (SEM), and conditions were set such that collapse of theconcavo-convex pattern was not observed. As a result, the obtainedconditions are as follows.

-   -   The entire chamber reaches the critical temperature of FC-72        (when a liquid other than FC-72 is used, the critical        temperature of the liquid).    -   The entire liquid in the chamber changes to a critical fluid or        gas.    -   After supercritical processing, the pressure inside the chamber        is reduced at a low speed (2 MPa/min or less).

The following examples and comparative examples were carried outaccording to the conditions obtained in Reference Example 1.

Example 1

A silicon wafer having a concavo-convex pattern composed of convexportions and concave portions formed on its surface was sequentiallyimmersed in deionized water (DIW) and isopropyl alcohol (IPA), and thentaken out. The taken-out silicon wafer was immersed in about 2.5 mL ofIPA in a test tube. Then, about 23 mL of hydrochlorofluoroolefin (HCFO)was added to the test tube. The HCFO used is CCK-1105 manufactured byCentral Glass Co., Ltd. The common name for CCK-1105 istrans-1-chloro-3,3,3-trifluoropropene ((E)-CF₃CH═CHCl), and its alias isHCFO-1233zdE. CCK-115 has a boiling point of 18.4° C., a criticaltemperature of 167° C., a critical pressure of 3.6 MPa, and a GWP of 1,is in a liquid state at room temperature and a pressure near atmosphericpressure (0.2 MPa), and is miscible with IPA. After the addition ofCCK-1105, the test tube was introduced into the chamber, and asupercritical processing was performed in the chamber. The supercriticalprocessing was performed by maintaining the temperature and pressureinside the chamber at 200° C. and 4.8 MPa for 20 minutes, respectively.The critical temperature (calculated value) of the mixed liquid of IPAand CCK-1105 (IPA:CCK-1105=1:10 (volume ratio)) is 182° C., and thecritical pressure (calculated value) is 4 MPa. After the supercriticalprocessing, the inside of the chamber was depressurized, and the siliconwafer was taken out from the test tube. After the supercriticalprocessing, the concavo-convex pattern on the surface of the siliconwafer was observed by a scanning electron microscope (SEM) to calculatethe collapse rate of the concavo-convex pattern (collapsedconcavo-convex pattern/all concavo-convex pattern×100). As a result, thecollapse rate of the concavo-convex pattern was 0.8%.

Example 2

In Example 2, it was confirmed that the collapse suppressing effect ofthe concavo-convex pattern was different between the case of usingCCK-1105 alone and the case of using a mixed liquid of IPA and CCK-1105.

(1) A silicon wafer having a concavo-convex pattern composed of convexportions and concave portions formed on its surface was placed in a testtube. Then, about 25 mL of a mixed liquid of IPA and CCK-1105(IPA:CCK-1105=1:10 (volume ratio)) was added, and the silicon wafer wasimmersed in the mixed liquid of IPA and CCK-1105. The boiling point ofthe mixture of IPA and CCK-1105 is higher than the boiling point ofCCK-1105 (18.4° C.). After the addition of the mixed liquid of IPA andCCK-1105, the test tube was introduced into the chamber, and asupercritical processing was performed in the chamber. The supercriticalprocessing was performed by maintaining the temperature and pressureinside the chamber at 200° C. and 4.8 MPa for 15 minutes, respectively.The critical temperature (calculated value) of the mixed liquid of IPAand CCK-1105 (IPA:CCK-1105=1:10 (volume ratio)) is 182° C., and thecritical pressure (calculated value) is 4 MPa. After the supercriticalprocessing, the inside of the chamber was depressurized, and the siliconwafer was taken out from the test tube. After the supercriticalprocessing, the concavo-convex pattern on the surface of the siliconwafer was observed by a scanning electron microscope (SEM) to calculatethe collapse rate of the concavo-convex pattern (collapsedconcavo-convex pattern/all concavo-convex pattern×100). As a result, thecollapse rate of the concavo-convex pattern was 1.5%.

(2) A silicon wafer having a concavo-convex pattern composed of convexportions and concave portions formed on its surface was placed in a testtube. Then, about 25 mL of CCK-1105 was added alone, and the siliconwafer was immersed in CCK-1105. After the addition of CCK-1105, the testtube was introduced into the chamber, and a supercritical processing wasperformed in the chamber. The supercritical processing was performed bymaintaining the temperature and pressure inside the chamber at 200° C.and 4.8 MPa for 15 minutes, respectively. The critical temperature ofCCK-1105 is 167° C., and the critical pressure (calculated value) is 3.6MPa. After the supercritical processing, the inside of the chamber wasdepressurized, and the silicon wafer was taken out from the test tube.After the supercritical processing, the concavo-convex pattern on thesurface of the silicon wafer was observed by a scanning electronmicroscope (SEM) to calculate the collapse rate of the concavo-convexpattern (collapsed concavo-convex pattern/all concavo-convexpattern×100). As a result, the collapse rate of the concavo-convexpattern was 75.1%.

In the case where CCK-1105 was used alone, when CCK-1105 was added tothe test tube, the silicon wafer was partially dried and theconcavo-convex pattern was collapsed as soon as the first drop ofCCK-1105 strikes the silicon wafer. In contrast, since the boiling pointof the mixed liquid of IPA and CCK-1105 is higher than the boiling pointof CCK-1105 (18.4° C.), using the mixed liquid of IPA and CCK-1105 didnot cause collapse of the concavo-convex pattern, which occurred whenCCK-1105 was used alone. Accordingly, in the case where HCFO having aboiling point lower than room temperature is used, it is desirable touse a mixed liquid of HCFO and an organic solvent having a higherboiling point than that of HCFO to enhance the collapse suppressingeffect, as compared with using HCFO alone.

Example 3

The same operation as in (1) of Example 2 was carried out except thatthe temperature and the pressure in the chamber were set to (A) 164° C.and 3 MPa, (b) 171° C. and 3.6 MPa, (c) 182° C. and 4.2 MPa, (d) 192° C.and 4.5 MPa, (e) 200° C. and 4.8 MPa, (f) 155° C. and 2.5 MPa, and (g)147° C. and 1.8 MPa. As a result, the collapse rate of theconcavo-convex pattern was 2.4% in (a), 1.2% in (b), 0.4% in (c), 2.6%in (d), 1.8% in (e), 97.3% in (f), and 100% in (g). Considering that thecritical temperature (calculated value) of the mixed liquid of IPA andCCK-1105 (IPA:CCK-1105=1:10 (volume ratio)) is 182° C. and the criticalpressure (calculated value) is 4 MPa, the mixed liquid of IPA andCCK-1105 may be changed to a supercritical fluid or a subcritical fluidin the conditions of a) to (e), which result in a high effect ofsuppressing collapse of the concavo-convex pattern. In contrast, themixed liquid of IPA and CCK-1105 may not be changed to a supercriticalfluid or a subcritical fluid in the conditions (f) and (g), which resultin a low effect of suppressing collapse of the concavo-convex pattern.

Example 4

The same operation as in Example 1 was carried out except that acommercially available hydrofluoroolefin (hereinafter referred to as“Hydrofluoroolefin A”) was used in place of CCK-1105, and thesupercritical processing was performed by maintaining the temperatureand pressure in the chamber at 266° C. and 2.7 MPa for 20 minutes,respectively. The critical temperature of Hydrofluoroolefin A is 240°C., and the critical pressure (calculated value) is 1.8 MPa. After thesupercritical processing, the concavo-convex pattern on the surface ofthe silicon wafer was observed by a scanning electron microscope (SEM).As a result, tapering of the concavo-convex pattern was observed. It isconsidered that the oxide film on the Si surface was etched by fluorinedue to the difference in Si pillar diameter before and after thesupercritical processing. It is thought that this fluorine was generatedby hydrolysis of a low molecular weight ether component contained inHydrofluoroolefin A. Although the amount of the fluorine generated isextremely small, it is considered that pattern damage occurred at alevel that is visually discriminable because the chemical reaction waspromoted under the high temperature and high pressure conditions in thesupercritical process.

Example 5

A silicon wafer having a concavo-convex pattern composed of convexportions and concave portions formed on its surface was sequentiallyimmersed in deionized water (DIW) and isopropyl alcohol (IPA), and thentaken out. The taken-out silicon wafer was immersed in about 2.5 mL ofIPA in a test tube. Then, about 23 mL of diisopropyl ether (DIPE) wasadded to the test tube. After the addition of DIPE, the test tube wasintroduced into the chamber, and a supercritical processing wasperformed in the chamber. The supercritical processing was performed bymaintaining the temperature and pressure inside the chamber at 224° C.and 2.8 MPa for 20 minutes, respectively. Incidentally, 224° C. is atemperature near the critical temperature (227° C.) of DIPE, and 2.8 MPais a pressure near the critical pressure (2.9 MPa) of DIPE. After thesupercritical processing, the inside of the chamber was depressurized,and the silicon wafer was taken out from the test tube.

A large amount of viscous substances were adhered to the silicon waferafter the supercritical processing. Thus, observation of theconcavo-convex pattern on the surface of the silicon wafer by thescanning electron microscope (SEM) was not performed.

Since DIPE generates a self-degradable and explosive component calledorganic peroxide by autoxidation in the atmosphere, an antioxidant(e.g., dibutyl hydroxytoluene (BHT)) is usually added to DIPE. It isconsidered that, since the boiling point (265° C.) of BHT is higher thanthe critical temperature (227° C.) of DIPE, BHT is not evaporated duringthe supercritical processing but is condensed, so that the viscoussubstance is generated as a residue.

Example 6

The same operation as in Example 1 was carried out except that acommercially available methyl tert-butyl ether (MTBE) was used in placeof DIPE, and the supercritical processing was performed by maintainingthe temperature and pressure in the chamber at 260° C. and 5.8 MPa for20 minutes, respectively. Incidentally, 260° C. is a temperature higherthan the critical temperature (224° C.) of MTBE, and 5.8 MPa is apressure higher than the critical pressure (3.4 MPa) of MTBE.

After the supercritical processing, the concavo-convex pattern on thesurface of the silicon wafer was observed by a scanning electronmicroscope (SEM). As a result, collapse of the concavo-convex patternwas slightly observed at the end portion of the silicon wafer, butcollapse of the concavo-convex pattern was not observed in otherportions.

In addition, adhesion of viscous substances observed in DIPE was notobserved. Unlike DIPE, MTBE is hardly auto-oxidized in the atmosphere.Thus, it is not necessary to add an antioxidant such as BHT thereto.Therefore, 99.8% purity MTBE (high performance liquid chromatographygrade) may be commercially available, and adhesion of viscous substancesmay be suppressed by using such a high purity MTBE.

Further, MTBE does not contain fluorine, and no fluorine is generated bythe supercritical processing. Thus, pattern damage due to fluorine wasnot observed.

Comparative Example 1

The same operation as in Example 1 was carried out except that acommercially available hydrofluoroolefin (hereinafter referred to as“Hydrofluoroolefin A”) was used in place of DIPE, and the supercriticalprocessing was performed by maintaining the temperature and pressure inthe chamber at 266° C. and 2.7 MPa for 20 minutes, respectively.Incidentally, 260° C. is a temperature higher than the criticaltemperature (240° C.) of Hydrofluoroolefin A, and 2.7 MPa is a pressurehigher than the critical pressure (1.8 MPa) of the hydrofluoroolefin.

After the supercritical processing, the concavo-convex pattern on thesurface of the silicon wafer was observed by a scanning electronmicroscope (SEM). As a result, tapering of the concavo-convex patternwas observed. It is considered that the oxide film on the Si surface wasetched by fluorine due to the difference in Si pillar diameter beforeand after the supercritical processing. It is thought that this fluorinewas generated by hydrolysis of a low molecular weight ether componentcontained in Hydrofluoroolefin A. Although the amount of the fluorinegenerated is extremely small, it is considered that pattern damageoccurred at a level that is visually discriminable because the chemicalreaction was promoted under the high temperature and high pressureconditions in the supercritical process.

From the foregoing, it will be appreciated that various embodiments ofthe present disclosure have been described herein for purposes ofillustration, and that various modifications may be made withoutdeparting from the scope and spirit of the present disclosure.Accordingly, the various embodiments disclosed herein are not intendedto be limiting, with the true scope and spirit being indicated by thefollowing claims.

What is claimed is:
 1. A substrate processing method for drying asubstrate in a chamber, the substrate processing method comprising:supplying a processing liquid that contains hydrofluoroolefin and isstored in a reservoir to the substrate, before the substrate isaccommodated in the chamber at a position external to the chamber;regenerating a liquid from a gas evaporated from the processing liquidsupplied to the substrate in the supplying while the substrate is in theposition external to the chamber; moving the substrate to beaccommodated in the chamber; heating an inside of the chamber in a statewhere the substrate is accommodated in the chamber and closing thechamber such that a vapor pressure of the processing liquid, as theprocessing liquid is heated, pressurizes the chamber to change theprocessing liquid supplied to the substrate into a subcritical fluidwhen a temperature-pressure state of the chamber approaches a criticaltemperature and pressure of the processing liquid, or a supercriticalfluid when the temperature-pressure state of the chamber exceeds thecritical temperature and pressure of the processing liquid; dischargingthe supercritical fluid or the subcritical fluid from the chamber; andregenerating a liquid from the discharged supercritical fluid orsubcritical fluid.
 2. The substrate processing method of claim 1,wherein the hydrofluoroolefin is hydrochlorofluoroolefin.
 3. Thesubstrate processing method of claim 1, further comprising: supplyingthe regenerated liquids to the reservoir.
 4. The substrate processingmethod of claim 3, further comprising: adjusting a concentration of theprocessing liquid stored in the reservoir to a predeterminedconcentration after the regenerated liquids are supplied to thereservoir.
 5. The substrate processing method of claim 1, wherein theprocessing liquid contains an organic solvent having a boiling pointhigher than that of the hydrofluoroolefin.
 6. The substrate processingmethod of claim 5, wherein a dry preventing liquid for prevent drying ofthe substrate is supplied to a surface of the substrate before theprocessing liquid is supplied to the surface of the substrate, the drypreventing liquid contains an organic solvent, and the organic solventcontained in the dry preventing liquid and the organic solvent containedin the processing liquid are the same.
 7. The substrate processingmethod of claim 1, further comprising: cooling the processing liquidstored in the reservoir.
 8. A non-transitory computer-readable storagemedium that stores a program for controlling a substrate processingapparatus which, when executed, cause a computer to control thesubstrate liquid processing apparatus and execute the substrate liquidprocessing method of claim
 1. 9. A substrate processing method fordrying a substrate in a chamber, comprising: supplying a liquid dialkylether represented by R¹—O—R² (wherein R¹ and R² represent the same ordifferent alkyl groups) to the substrate unit before the substrate isaccommodated in the chamber at a position external to the chamber;regenerating a liquid from a gas evaporated from the liquid dialkylether supplied to the substrate in the supplying while the substrate isin the position external to the chamber; moving the substrate to beaccommodated in the chamber; heating an inside of the chamber in a statewhere the substrate is accommodated in the chamber and closing thechamber such that a vapor pressure of the liquid dialkyl ether, as theliquid dialkyl ether is heated, pressurizes the chamber to change theliquid dialkyl ether supplied to the substrate into a subcritical fluidwhen a temperature-pressure state of the chamber approaches a criticaltemperature and pressure of the liquid dialkyl ether, or a supercriticalfluid when the temperature-pressure state of the chamber exceeds thecritical temperature and pressure of the liquid dialkyl ether;discharging the supercritical fluid or the subcritical fluid from thechamber; and regenerating a liquid from the discharged supercriticalfluid or subcritical fluid.
 10. The substrate processing method of claim9, wherein the liquid dialkyl ether is methyl tert-butyl ether.
 11. Thesubstrate processing method of claim 9, wherein a dry preventing liquidis supplied to a surface of the substrate before the liquid dialkylether is supplied.
 12. The substrate processing method of claim 11,wherein the dry preventing liquid contains isopropyl alcohol.
 13. Thesubstrate processing method of claim 11, wherein the dry preventingliquid contains propylene glycol monomethyl ether acetate.
 14. Anon-transitory computer-readable storage medium that stores a programfor controlling a substrate processing apparatus which, when executed,cause a computer to control the substrate liquid processing apparatusand execute the substrate liquid processing method of claim 9.